Structurally-Colored Filaments and Methods for Making and Using Structurally-Colored Filaments

ABSTRACT

The present disclosure are directed to objects having an optical element that imparts structural color.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to, co-pending U.S. Patent Applicationentitled “STRUCTURALLY-COLORED FILAMENTS AND METHODS FOR MAKING ANDUSING STRUCTURALLY-COLORED FILAMENTS,” filed on Mar. 27, 2019, andassigned application number 62/824,632, and claims priority to,co-pending U.S. Patent Application entitled “STRUCTURALLY-COLOREDFILAMENTS AND METHODS FOR MAKING AND USING STRUCTURALLY-COLOREDFILAMENTS,” filed on Oct. 17, 2019, and assigned application No.62/916,296, both of which are incorporated herein by reference in theirentireties.

BACKGROUND

Structural color is caused by the physical interaction of light with themicro- or nano-features of a surface and the bulk material as comparedto color derived from the presence of dyes or pigments that absorb orreflect specific wavelengths of light based on the chemical propertiesof the dyes or pigments. Color from dyes and pigments can be problematicin a number of ways. For example, dyes and pigments and their associatedchemistries for fabrication and incorporation into finished goods maynot be environmentally friendly.

BRIEF DESCRIPTION OF THE DRAWINGS

Further embodiments of the present disclosure will be more readilyappreciated upon review of the detailed description of its variousembodiments, described below, when taken in conjunction with theaccompanying drawings.

FIGS. 1A-1M shows various articles of footwear, apparel, athleticequipment, container, electronic equipment, and vision wear that includethe structure in accordance with the present disclosure, while FIGS.1N-1P illustrate additional details regarding different types offootwear.

FIG. 2A illustrates a side view of exemplary inorganic optical elementof the present disclosure. FIG. 2B illustrates a side view of exemplaryinorganic optical element of the present disclosure.

DESCRIPTION

The present disclosure provides for filaments (structural color filamentor “SC” filament) that comprise optical elements or fragments thereofthat impart an optical effect (e.g., a structural color, a metallicappearance, or an iridescent appearance), where the optical elements arerandomly dispersed throughout and on the surface of the SC filament. Theoptical effect imparted to the SC filament produces an aestheticallyappealing appearance without requiring the use of inks or pigments andthe environmental impact associated with their use. The optical effectfrom the optical element or fragments thereof is produced, at least inpart, through scattering, refraction, reflection, interference, and/ordiffraction of visible wavelengths of light. The optical effect caninclude structural color (e.g., hues of blue, green, red, yellow, andthe like), where a subset of the structural color can be an iridescentor metallic appearance. Yarn or fiber can be formed using the SCfilament and optionally other types of filaments.

The SC filament can be produced by melting a plurality of structurallycolored articles and then extruding the molten material to form the SCfilament, where the optical element or fragments thereof are dispersedthroughout and on the surface of the SC filament. The structurallycolored article can include a thermoplastic material and a plurality ofthe optical elements and fragments thereof. Depending upon how thestructurally colored articles are produced and/or the processing of thestructurally color article (e.g., the extrusion process), the SCfilament can include intact optical elements as originally produced orfragments thereof, where the optical elements and fragments thereof canimpart the optical effect.

The structurally colored articles can include pellets, films, sheets,and the like where each can be extruded articles. The structurallycolored articles can be formed by disposing (e.g., affixing, attaching,adhering, bonding, joining) the optical element directly onto anarticle. Alternatively, the structurally colored articles can be formedby processing (e.g., grinding, cutting, shredding, crushing, or acombination thereof) a polymer-based item that includes a thermoplasticmaterial and at least one optical element. During the processing of thepolymer-based item, fragments of one or more optical elements can beformed, where all or some of the optical elements or fragments thereofretain the characteristic to impart the optical effect. The pieces ofthe polymer-based item are melted to form a molten material. The moltenmaterial is extruded to form the structurally colored articles. Theoptical elements and/or fragments thereof from the processing step canalso form other fragments during the extrusion process. The opticalelement and/or fragments of optical elements impart the optical effectto the structurally colored articles. The optical effect before andafter processing and/or extrusion may be the same or different.

The optical element or fragments of the optical element can include atleast one optical layer optionally having a textured surface (e.g.,integral to the optical element or as part of the surface of thearticle), optionally with a protective layer, or optionally with anycombination of the textured surface and the protective layer. Theoptical element can be a single layer reflector, a single layer filter,a multilayer reflector or a multilayer filter. The optical elements orfragments of the optical element on the surface of the filaments causethe article incorporating the filament to have the optical effect thatcan be different than the article with a filament without the opticalelements or fragments of the optical element.

The present disclosure provides a method of making a structural color(SC) filament, comprising melting a plurality of structurally coloredarticles, each structurally colored article comprising a thermoplasticmaterial and a plurality of optical elements or fragments thereof, toform a first molten material including the plurality of optical elementsor fragments thereof dispersed therein; and extruding the first moltenmaterial to form the SC filament, wherein the SC filament includes thedispersed plurality of optical elements or fragments thereof, and thedispersed plurality of optical elements or fragments thereof impart anoptical effect to the SC filament. The present disclosure also providesan article comprising the SC filament made according to the method aboveand herein. The article can be an article of footwear, an article ofapparel, or an article of sporting equipment.

The present disclosure provides for an article, comprising a SC filamenthaving a plurality of optical elements and the fragments thereofrandomly distributed throughout the SC filament, wherein the pluralityof optical elements and the fragments thereof impart an optical effectto the filament.

The present disclosure provides for a method of forming an item,comprising: processing thereof a polymer-based item comprising at leastone optical element to form pieces of the polymer-based item, whereinthe optical element imparts a first optical effect to the polymer-baseditem, wherein a portion of at least one optical element is ground or cutinto fragments of the optical element, wherein a first portion of thepieces of the polymer-based item retain the characteristic to impart thefirst optical effect; melting the pieces of the polymer-based item toform a second molten material; and extruding the second molten materialto form structurally colored articles comprising the optical element andfragments thereof, wherein a portion of the optical elements and/or thefragments thereof impart a second optical effect to the structurallycolored articles.

The present disclosure provides for a method of forming structurallycolored item, comprising: disposing an optical element onto a pellet forform a structurally colored pellet, wherein the optical element impartsan optical effect to the structurally colored pellets.

While in many examples of this disclosure, the optical effect can be astructural color such as iridescent (e.g., iridescent structural color,a color which shifts over a wide range of hues when viewed fromdifferent angles), metallic, or a “color” (e.g., non-iridescent ornon-metallic) as described herein. In regard to an aspect where thestructural color is not iridescent or metallic, the structural color canbe of the type which does not shift over a wide range of hues whenviewed from different angles (e.g., a structural color which does notshift hues, or which shifts over a limited number of hues depending uponthe viewing angle). In one example, the present disclosure provides forthe optical element or fragments of the optical element, when measuredaccording to the CIE 1976 color space under a given illuminationcondition at three observation angles of about −15 to 180 degrees orabout −15 degrees and +60 degrees, has a first color measurement at afirst angle of observation having coordinates L₁* and a₁* and b₁*, and asecond color measurement at a second angle of observation havingcoordinates L₂* and a₂* and b₂*, and a third color measurement at athird angle of observation having coordinates L3* and a₃* and b₃*,wherein the L₁*, L₂*, and L3* values may be the same or different,wherein the a₁*, a₂*, and a₃* coordinate values may be the same ordifferent, wherein the b₁*, b₂*, and b₃* coordinate values may be thesame or different, and wherein the range of the combined a₁*, a₂* anda₃* values is less than about 40% of the overall scale of possible a*values.

In another example, the present disclosure provides for the opticalelement, when measured according to the CIE 1976 color space under agiven illumination condition at two observation angles of about −15 to180 degrees or about −15 degrees and +60 degrees, has a first colormeasurement at a first angle of observation having coordinates L₁* anda₁* and b₁*, and a second color measurement at a second angle ofobservation having coordinates L₂* and a_(z)* and b₂*, wherein the L₁*and L₂* values may be the same or different, wherein the a₁* and a₂*coordinate values may be the same or different, wherein the b₁* and b₂*coordinate values may be the same or different, and wherein the ΔE*abbetween the first color measurement and the second color measurement isless than or equal to 10, whereΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²]^(1/2) or alternativelygreater than 10.

In yet another example, the present disclosure provides for the opticalelement, when measured according to the CIELCH color space under a givenillumination condition at three observation angles of about −15 to 180degrees or about −15 degrees and +60 degrees, has a first colormeasurement at a first angle of observation having coordinates L₁* andC₁* and h₁°, and a second color measurement at a second angle ofobservation having coordinates L₂* and C₂* and h₂°, and a third colormeasurement at a third angle of observation having coordinates L₃* andC₃* and h₃°, wherein the L₁*, L₂*, and L₃* values may be the same ordifferent, wherein the C₁*, C₂*, and C₃* coordinate values may be thesame or different, wherein the h₁°, h₂° and h₃° coordinate values may bethe same or different, and wherein the range of the combined h₁°, h₂°and h₃° values is less than about 10 degrees or alternatively greaterthan 10 degrees.

The present disclosure will be better understood upon reading thefollowing numbered aspects, which should not be confused with theclaims. Any of the numbered aspects below can, in some instances, becombined with aspects described elsewhere in this disclosure and suchcombinations are intended to form part of the disclosure.

-   Aspect 1. A method of making a structural color (SC) filament,    comprising

melting a plurality of structurally colored articles, each structurallycolored article comprising a thermoplastic material and a plurality ofoptical elements or fragments thereof, to form a first molten materialincluding the plurality of optical elements or fragments thereofdispersed therein; and

extruding the first molten material to form the SC filament, wherein theSC filament includes the dispersed plurality of optical elements orfragments thereof, and the dispersed plurality of optical elements orfragments thereof impart an optical effect to the SC filament.

-   Aspect 2. The method of the preceding aspect, wherein the optical    element of each structurally colored article is a coating on the    structurally colored article.-   Aspect 3. The method of any one of the preceding aspects, wherein    the structurally colored article is a pellet, optionally an extruded    pellet.-   Aspect 4. The method of any one of the preceding aspects, wherein    the structurally colored article is a ground, crushed or shredded    structurally colored article.-   Aspect 5. The method of any one of the preceding aspects, wherein    the ground, crushed or shredded structurally colored article is a    film or sheet.-   Aspect 6. The method of any one of the preceding aspects, wherein    the ground, crushed or shredded structurally colored article is a    ground structurally colored container, optionally a ground, crushed    or shredded structurally colored bottle.-   Aspect 7. The method of any one of the preceding aspects, wherein    the optical element and the fragments thereof are layered structures    having two or more layers stacked in the z dimension, optionally the    optical element and the fragments thereof have a width in the x    dimension, a length in the y dimension and a thickness in the z    dimension, wherein the thickness of the plurality of optical    elements the fragments thereof dispersed in the filament are less    than 10 percent less than the thickness of the plurality of optical    element and the fragments thereof on the structurally colored    article, and optionally the width and length of the portions of the    plurality of optical elements and the fragments thereof dispersed in    the filament are at least 5 percent smaller than the width and    length of the plurality of optical elements and the fragments    thereof of the structurally colored article.-   Aspect 8. The method of any one of the preceding aspects, wherein    the plurality of optical elements and the fragments thereof    dispersed in the filament optionally has, independently, an average    width and an average length of about 400 nanometers or more, about    500 nanometer or more, or about 800 nanometers or more; wherein the    plurality of optical elements and the fragments thereof dispersed in    the filament has an average width and an average length of about 400    nanometers or more, about 500 nanometer or more, or about 800    nanometers or more; and optionally wherein the plurality of    dispersed optical elements and the fragments thereof in the filament    has an average thickness of about 200 nanometers or more, about 250    nanometers or more, about 300 nanometers or more, about 350    nanometers for more, about 400 nanometers or more about 500    nanometers or more, about 600 nanometers or more, about 800    nanometers or more.-   Aspect 9. The method of any one of the preceding aspects, wherein    the optical element on the structurally colored article is a    structurally colored coating covering at least 25 percent or at    least 50 percent or at least 75 percent of a total surface area of    the structurally colored article, and optionally the portions of the    plurality of optical elements the fragments thereof dispersed in the    filament are a plurality of fragments formed from grinding,    crushing, shredding, melting, or a combination thereof of the    structurally colored article.-   Aspect 10. The method of any one of the preceding aspects, wherein    the plurality of optical elements and the fragments thereof make up    at least 1 percent by weight or at least 2 percent by weight or at    least 5 percent by weight or at least 7 percent by weight or at    least 10 percent by weight of a total weight of the filament.-   Aspect 11. The method of any one of the preceding aspects, wherein a    portion of the plurality of optical elements and the fragments    thereof are not structurally deteriorated during melting, extruding,    or both so that they do not impart the optical effect.-   Aspect 12. The method of any one of the preceding aspects, wherein a    portion of the plurality of optical elements and the fragments    thereof are structurally deteriorated during melting, extruding, or    both so that they do not impart the optical effect.-   Aspect 13. The method of any one of the preceding aspects, wherein    the method further comprises processing the structurally colored    polymeric material prior to the melting, wherein optionally    processing comprises grinding, shredding, cutting, or crushing.-   Aspect 14. An article comprising, the SC filament made according to    any one of aspects 1-13.-   Aspect 15. The article of the preceding aspect, wherein the article    is an article of footwear, an article of apparel, or an article of    sporting equipment.-   Aspect 16. An article, comprising a SC filament having a plurality    of optical elements and the fragments thereof randomly distributed    throughout the SC filament, wherein the plurality of optical    elements and the fragments thereof impart an optical effect to the    filament.-   Aspect 17. The article of any one of the preceding aspects, wherein    the optical effect is a structural color and is not iridescent or    metallic.-   Aspect 18. The article of any one of the preceding aspects, wherein    the optical effect is an iridescent appearance.-   Aspect 19. The article of any one of the preceding aspects, wherein    the optical effect is a metallic appearance.-   Aspect 20. The article of any one of the preceding aspects, wherein    the optical element and the fragments thereof are layered structures    that has two or more layers stacked in a z dimension perpendicular    to the plane of the layered structures.-   Aspect 21. The article of any one of the preceding aspects, wherein    the plurality of optical elements and the fragments thereof    dispersed in the SC filament optionally has, individually, an    average width and an average length of about 400 nanometers or more,    about 500 nanometer or more, or about 800 nanometers or more;    wherein the plurality of optical elements and the fragments thereof    dispersed in the filament has an average width and an average length    of about 400 nanometers or more, about 500 nanometer or more, or    about 800 nanometers or more; and optionally wherein the plurality    of dispersed optical elements and the fragments thereof in the    filament has an average thickness of about 200 nanometers or more,    about 250 nanometers or more, about 300 nanometers or more, about    350 nanometers for more, about 400 nanometers or more about 500    nanometers or more, about 600 nanometers or more, about 800    nanometers or more.-   Aspect 22. The article of any one of the preceding aspects, wherein    the plurality of optical elements and the fragments thereof make up    at least 1 percent by weight, or at least 2 percent by weight, or at    least 5 percent by weight, or at least 7 percent by weight, or at    least 10 percent by weight of a total weight of the filament.-   Aspect 23. The article of any one of the preceding aspects, wherein    the plurality of the optical elements and the fragments thereof on    the SC filament covers at least 25 percent, or at least 50 percent,    or at least 75 percent of a total surface area of the filament.-   Aspect 24. The method or article of any one of the preceding    aspects, wherein the optical effect is a structural color and not    iridescent or metallic.-   Aspect 25. The method or article of any one of the preceding    aspects, wherein the optical effect is an iridescent appearance.-   Aspect 26. The method or article of any one of the preceding    aspects, wherein the optical effect is a metallic appearance.-   Aspect 27. The method or article of any one of the preceding    aspects, wherein the optical effect imparts two or more different    hues to the filament when the filament is viewed from at least two    different angles 15 degrees apart.-   Aspect 28. The method or article of any one of the preceding    aspects, wherein the optical effect imparted to the filament is    visible to a viewer having 20/20 visual acuity and normal color    vision from a distance of about 1 meter from the article.-   Aspect 29. The method or article of any one of the preceding    aspects, further comprising forming a fiber or a yarn, wherein the    fiber or yarn comprises the SC filament.-   Aspect 30. The method or article of any one of the preceding    aspects, wherein the yarn is a monofilament yarn or a multi-filament    yarn.-   Aspect 31. The method or article of any one of the preceding    aspects, wherein the yarn is a staple yarn including a plurality of    staple fibers formed by cutting or chopping the SC filament.-   Aspect 32. The method or article of any one of the preceding    aspects, wherein the filament is present in a staple yarn, a    monofilament yarn, or a multifilament yarn; optionally wherein the    yarn has a tenacity of about 1.5 grams per Denier to about 4.0 grams    per Denier; or has tenacity of greater than 4.0 grams per Denier; or    has a tenacity of about 5.0 grams per Denier to about 10 grams per    Denier.-   Aspect 33. The method or article of any one of the preceding    aspects, wherein the SC filament of a staple fiber has an aspect    ratio of 10 to 100,000.-   Aspect 34. The method or article of any one of the preceding    aspects, wherein the SC filament is present in the form of a    textile, and optionally wherein the textile is a non-woven textile,    a woven textile, a knit textile, a braided textile, or a crocheted    textile.-   Aspect 35. The method or article of any one of the preceding    aspects, wherein the SC filament is attached to a substrate,    optionally wherein the SC filament is stitched to or embroidered to    the substrate.-   Aspect 36. The method or article of any one of the preceding    aspects, wherein the SC filament is included with a plurality of    second filaments in the form of a tow.-   Aspect 37. The method or article of any one of the preceding    aspects, wherein the plurality of second filaments of the tow are    substantially free of optical elements.-   Aspect 38. The method or article of any one of the preceding    aspects, wherein the plurality of second filaments of the tow    comprise second optical elements imparting a second optical effect    to the second filaments.-   Aspect 39. The method or article of any one of the preceding    aspects, wherein the second optical effect of the plurality of    second filaments is a different type of optical effect than the    optical effect of the SC filament.-   Aspect 40. The method or article of any one of the preceding    aspects, further comprising dying the SC filament, fibers comprising    the SC filament, or yarn comprising the SC filament.-   Aspect 41. The method or article of any one of the preceding    aspects, wherein the structurally colored thermoplastic material    comprises at least one thermoplastic polymer, optionally wherein the    at least one thermoplastic polymer includes a thermoplastic    elastomer.-   Aspect 42. The method or article of any one of the preceding    aspects, wherein melting includes increasing a temperature of the    thermoplastic material to a first temperature at or above a melting    temperature of the thermoplastic polymer.-   Aspect 43. The method or article of any one of the preceding    aspects, wherein the thermoplastic material includes one or more    thermoplastic polyurethanes, thermoplastic polyethers, thermoplastic    polyesters, thermoplastic polyamides, thermoplastic polyolefins,    thermoplastic co-polymers thereof, or a combination thereof.-   Aspect 44. The method or article of any one of the preceding    aspects, wherein the optical element includes at least one optical    layer.-   Aspect 45. The method or article of any one of the preceding    aspects, wherein the optical element is single layer reflector, a    single layer filter, a multilayer reflector or a multilayer filter.-   Aspect 46. The method or article of any one of the preceding    aspects, wherein the multilayer reflector has at least two layers,    including at least two adjacent layers having different refractive    indices.-   Aspect 47. The method or article of any one of the preceding    aspects, wherein at least one of the layers of the multilayer    reflector has a thickness that is about one-fourth of the wavelength    of visible light.-   Aspect 48. The method or article of any one of the preceding    aspects, wherein at least one of the layers of the multilayer    reflector comprises a material selected from the group consisting    of: silicon dioxide, titanium dioxide, zinc sulfide, magnesium    fluoride, tantalum pentoxide, and a combination thereof.-   Aspect 49. The method or article of any one of the preceding    aspects, further comprising a textured surface on a first side of    the optical element.-   Aspect 50. The method or article of any one of the preceding    aspects, wherein the textured surface has a plurality of profile    features and a plurality of flat areas.-   Aspect 51. The method or article of any one of the preceding    aspects, wherein the textured surface includes a plurality of    profile features and flat planar areas, wherein the profile features    extend above the flat areas of the textured surface.-   Aspect 52. The method or article of any one of the preceding    aspects, wherein the dimensions of the profile features, a shape of    the profile features, a spacing among the plurality of the profile    features, in combination with the optical layer impart the    structural color.-   Aspect 53. The method or article of any one of the preceding    aspects, wherein the spacing among the profile features reduces    distortion effects of the profile features produced from interfering    with one another when imparting the structural color of the    structural colored pellet.-   Aspect 54. The method or article of any one of the preceding    aspects, wherein the profile features and the flat areas result in    at least one optical layer of the optical element having an    undulating topography, wherein the optical layer has a planar region    between neighboring depressions and/or elevations that is planar    with the flat planar areas of the textured surface.-   Aspect 55. The method or article of any one of the preceding    aspects, wherein the structural color of the structurally colored    pellets has the appearance of a single color or multiple colors.-   Aspect 56. The method or article of any one of the preceding    aspects, wherein the optical element or the fragments thereof    exhibits a color that, when measured according to the CIE 1976 color    space under a given illumination condition at three observation    angles of about −15 to 180 degrees or about −15 degrees and +60    degrees, has a first color measurement at a first angle of    observation having coordinates L₁* and a₁* and b₁*, and a second    color measurement at a second angle of observation having    coordinates L₂* and a₂* and b₂*, and a third color measurement at a    third angle of observation having coordinates L3* and a₃* and b₃*,    wherein the L₁*, L₂*, and L3* values may be the same or different,    wherein the a₁*, a₂*, and a₃* coordinate values may be the same or    different, wherein the b₁*, b₂*, and b₃* coordinate values may be    the same or different, and wherein the range of the combined a₁*,    a₂* and a₃* values is less than about 40% of the overall scale of    possible a* values, optionally is less than about 30% of the overall    scale of possible a* values, optionally is less than about 20% of    the overall scale of possible a* values, or optionally is less than    about 10% of the overall scale of possible a* values.-   Aspect 57. The method or article of any one of the preceding    aspects, wherein the optical element or the fragments thereof    exhibits a color that, when measured according to the CIE 1976 color    space under a given illumination condition at three observation    angles of about −15 to 180 degrees or about −15 degrees and +60    degrees, has a first color measurement at a first angle of    observation having coordinates L₁* and a₁* and b₁*, and a second    color measurement at a second angle of observation having    coordinates L₂* and a₂* and b₂*, and a third color measurement at a    third angle of observation having coordinates L₃* and a₃* and b₃*,    wherein the L₁*, L₂*, and L₃* values may be the same or different,    wherein the a₁*, a₂*, and a₃* coordinate values may be the same or    different, wherein the b₁*, b₂*, and b₃* coordinate values may be    the same or different, and wherein the range of the combined b₁*,    b₂* and b₃* values is less than about 40% of the overall scale of    possible b* values, optionally is less than about 30% of the overall    scale of possible b* values, optionally is less than about 20% of    the overall scale of possible b* values, or optionally is 10% of the    overall scale of possible b* values.-   Aspect 58. The method or article of any one of the preceding    aspects, wherein the optical element the fragments thereof exhibits    a color that, when measured according to the CIE 1976 color space    under a given illumination condition at two observation angles of    about −15 to 180 degrees or about −15 degrees and +60 degrees, has a    first color measurement at a first angle of observation having    coordinates L₁* and a₁* and b₁*, and a second color measurement at a    second angle of observation having coordinates L₂* and a₂* and b₂*,    wherein the L₁* and L₂* values may be the same or different, wherein    the a₁* and a₂* coordinate values may be the same or different,    wherein the b₁* and b₂* coordinate values may be the same or    different, and wherein the ΔE*_(ab) between the first color    measurement and the second color measurement is greater than or    equal to about 100, where ΔE*_(ab)=[(L₁*−L₂*)^(2 l +(a)    ₁*−a₂*)²+(b₁*b²*)²]^(1/2), optionally is greater than or equal to    about 80, or optionally is greater than or equal to about 60 or    alternatively less than 3 or less than 2.2, or less than 2.-   Aspect 59. The method or article of any one of the preceding    aspects, wherein the optical element exhibits a color that, when    measured according to the CIELCH color space under a given    illumination condition at three observation angles of about −15 to    180 degrees or about −15 degrees and +60 degrees, has a first color    measurement at a first angle of observation having coordinates L₁*    and C₁* and h₁°, and a second color measurement at a second angle of    observation having coordinates L₂* and C₂* and h₂°, and a third    color measurement at a third angle of observation having coordinates    L3* and C3* and h₃°, wherein the L₁*, L₂*, and L3* values may be the    same or different, wherein the C₁*, C₂*, and C₃* coordinate values    may be the same or different, wherein the h₁°, h₂° and h₃°    coordinate values may be the same or different, and wherein the    range of the combined h₁°, h₂° and h₃° values is greater than about    60 degrees, optionally is greater than about 50 degrees, optionally    is greater than about 40 degrees, optionally is greater than about    30 degrees, or optionally is greater than about 20 degrees or    alternatively less than 10 degrees or less than 5 degrees.-   Aspect 60. The method or article of one the preceding aspects,    wherein the optical effect is visible to a viewer having 20/20    visual acuity and normal color vision from a distance of about 1    meter from the article.-   Aspect 61. The method or article of one the preceding aspects,    wherein the structural color has a single hue.-   Aspect 62. The method or article of one the preceding aspects,    wherein the structural color includes two or more hues.-   Aspect 63. The method or article of one the preceding aspects,    wherein the structural color has limited iridescence.-   Aspect 64. The method or article of one the preceding aspects,    wherein the structural color is not iridescence.-   Aspect 65. The method or article of one the preceding aspects,    wherein the structural color has limited iridescence such that, when    each color visible at each possible angle of observation is assigned    to a single hue selected from the group consisting of the primary,    secondary and tertiary colors on the red yellow blue (RYB) color    wheel, all of the assigned hues fall into a single hue group,    wherein the single hue group is one of a) green-yellow, yellow, and    yellow-orange; b) yellow, yellow-orange and orange; c)    yellow-orange, orange, and orange-red; d) orange-red, and    red-purple; e) red, red-purple, and purple; f) red-purple, purple,    and purple-blue; g) purple, purple-blue, and blue; h) purple-blue,    blue, and blue-green; i) blue, blue-green and green; and j)    blue-green, green, and green-yellow.-   Aspect 66. The method or article of one the preceding aspects,    wherein the structural color having limited iridescence is limited    to two or three of the hues green-yellow, yellow, yellow-orange; or    the hues purple-blue, blue, and blue-green; or the hues orange-red,    red, and red-purple; or the hues blue-green, green, and    green-yellow; or the hues yellow-orange, orange, and orange-red; or    the hues red-purple, purple, and purple-blue.-   Aspect 67. The method or article of one of the preceding aspects,    wherein an article comprises the SC filament.-   Aspect 68. The method or article of one of the preceding aspects,    wherein the article or substrate is an article of footwear, an    article of apparel, or an article of sporting equipment.-   Aspect 69. A method of forming an item, comprising:

processing thereof a polymer-based item comprising at least one opticalelement to form pieces of the polymer-based item, wherein the opticalelement imparts a first optical effect to the polymer-based item,wherein a portion of at least one optical element is ground or cut intofragments of the optical element, wherein a first portion of the piecesof the polymer-based item retain the characteristic to impart the firstoptical effect;

melting the pieces of the polymer-based item to form a second moltenmaterial; and

extruding the second molten material to form structurally coloredarticles comprising the optical element and fragments thereof, wherein aportion of the optical elements and/or the fragments thereof impart asecond optical effect to the structurally colored articles.

-   Aspect 70. The method of any one of the preceding aspects, wherein    the first optical effect and the second optical effect are the same    or the first optical effect and the second optical effect are    different.-   Aspect 71. The method of any one of the preceding aspects, wherein    the structurally colored articles are pellets or SC filaments.-   Aspect 72. The method of any one of the preceding aspects, wherein    the polymer-based item is a film or sheet.-   Aspect 73. The method of any one of the preceding aspects, wherein    the polymer-based item article is a container, optionally a bottle.-   Aspect 74. The method of any one of the preceding aspects, wherein    the article is an article of footwear, an article of apparel, or an    article of sporting equipment-   Aspect 75. The method of any one of the preceding aspects, wherein    the optical element and the fragments thereof are layered structures    having two or more layers stacked in the z dimension, optionally the    optical element and the fragments thereof have a width in the x    dimension, a length in the y dimension and a thickness in the z    dimension, wherein the thickness of the optical elements and the    fragments thereof dispersed in the structurally colored article are    less than 10 percent less than the thickness of the optical element    and the fragments thereof on the polymer-based item, and optionally    the width and length of the portions of the optical elements and the    fragments thereof dispersed in the polymer-based item are at least 5    percent smaller than the width and length of the optical element of    the polymer-based item.-   Aspect 76. The method of any one of the preceding aspects, wherein    the plurality of optical elements and the fragments thereof    dispersed in the structurally colored article optionally has,    independently, an average width and an average length of about 400    nanometers or more, about 500 nanometer or more, or about 800    nanometers or more; wherein the plurality of optical elements and    the fragments thereof dispersed in the filament has an average width    and an average length of about 400 nanometers or more, about 500    nanometer or more, or about 800 nanometers or more; and optionally    wherein the thickness of the fragments of the optical elements and    the fragments thereof dispersed in the structurally colored articles    are less than 10 percent less than the thickness of the optical    element on the polymer-based item.-   Aspect 77. The method of any one of the preceding aspects, wherein    the plurality of fragments of the dispersed optical elements in the    structurally colored article has an average thickness of about 200    nanometers or more, about 250 nanometers or more, about 300    nanometers or more, about 350 nanometers for more, about 400    nanometers or more about 500 nanometers or more, about 600    nanometers or more, about 800 nanometers or more.-   Aspect 78. The method of any one of the preceding aspects, further    comprising extruding the second molten material with a third molten    material, wherein the third molten material can comprise a    thermoplastic material including one or more thermoplastic    polyurethanes, thermoplastic polyesters, thermoplastic polyamides,    thermoplastic polyolefins, thermoplastic co-polymers thereof, or a    combination thereof.-   Aspect 79. The method of any one of the preceding aspects, wherein a    portion of the optical elements and the fragments thereof are not    structurally deteriorated during processing, melting, extruding, or    a combination thereof.-   Aspect 80. The method of any one of the preceding aspects, wherein a    portion of the number of the fragments of the optical elements are    structurally deteriorated during processing, melting, extruding, or    a combination thereof.-   Aspect 81. The method of any one of the preceding aspects, wherein    processing includes grinding, cutting, shredding, crushing, or a    combination.-   Aspect 82. The method of the preceding aspect, wherein the    polymer-based item is a film.-   Aspect 83. The method of any one of the preceding aspects, wherein    the film has a thickness of about 3 nanometers to about 1    millimeter.-   Aspect 84. The method of any one of the preceding aspects, wherein    the pieces of the polymer-based item have a largest dimension of    about 0.05 millimeters mm to 20 millimeters.-   Aspect 85. The method of any one of the preceding aspects, wherein    the structurally colored pellets have a largest dimension of about    0.05 millimeters mm to 20 millimeters.-   Aspect 86. The method of any one of the preceding aspects, wherein    the polymer-based item comprise a thermoplastic polymer or an    elastomeric material, or an elastomeric thermoplastic material.-   Aspect 87. The method of any one of the preceding aspects, wherein    melting includes increasing a temperature of the thermoplastic    polymer to a first temperature above a melting of the thermoplastic    polymer, or an elastomeric material, or an elastomeric thermoplastic    material.-   Aspect 88. The method of any one of the preceding aspects, wherein    the thermoplastic material includes one or more thermoplastic    polyurethanes, thermoplastic polyesters, thermoplastic polyamides,    thermoplastic polyolefins, thermoplastic co-polymers thereof, or a    combination thereof.-   Aspect 89. The method of any one of the preceding aspects, wherein    the first optical effect and the second optical effect are,    independently, a structural color.-   Aspect 90. The method of any one of the preceding aspects, wherein    the first optical effect and the second optical effect have,    independently, an iridescent appearance.-   Aspect 91. The method of any one of the preceding aspects, wherein    the first optical effect and the second optical effect have,    independently, a metallic appearance.-   Aspect 92. The method of any one of the preceding aspects, wherein    the first optical effect and the second optical effect,    independently, impart two or more different hues when viewed from at    least two different angles 15 degrees apart.-   Aspect 93. The method of any one of the preceding aspects, wherein    the first optical effect and the second optical effect,    independently, imparted is visible to a viewer having 20/20 visual    acuity and normal color vision from a distance of about 1 meter from    the article or item.-   Aspect 94. The method of any one of the preceding aspects, further    comprising forming a fiber or a yarn, wherein the fiber or yarn    comprises the SC filament.-   Aspect 95. The method of any one of the preceding aspects, wherein    the yarn is a monofilament yarn or a multi-filament yarn.-   Aspect 96. The method of any one of the preceding aspects, wherein    the yarn is a staple yarn including a plurality of staple fibers    formed by cutting or chopping the SC filament.-   Aspect 97. The method of any one of the preceding aspects, wherein    the SC filament is present in a staple yarn, a monofilament yarn, or    a multifilament yarn; optionally wherein the yarn has a tenacity of    about 1.5 grams per Denier to about 4.0 grams per Denier; or has    tenacity of greater than 4.0 grams per Denier; or has a tenacity of    about 5.0 grams per Denier to about 10 grams per Denier.-   Aspect 98. The method of any one of the preceding aspects, wherein    the SC filament of a staple fiber has an aspect ratio of 10 to    100,000.-   Aspect 99. The method of any one of the preceding aspects, wherein    the SC filament is present in the form of a textile, and optionally    wherein the textile is a non-woven textile, a woven textile, a knit    textile, a braided textile, or a crocheted textile.-   Aspect 100. The method of any one of the preceding aspects, wherein    the SC filament is attached to a substrate, optionally wherein the    filament is stitched to or embroidered to the substrate.-   Aspect 101. The method of any one of the preceding aspects, wherein    the SC filament is included with a plurality of second filaments in    the form of a tow.-   Aspect 102. The method of any one of the preceding aspects, wherein    the plurality of second filaments of the tow are substantially free    of optical elements.-   Aspect 103. The method of any one of the preceding aspects, wherein    the plurality of second filaments of the tow comprise second optical    elements imparting a second optical effect to the second filaments.-   Aspect 104. The method of any one of the preceding aspects, wherein    the second optical effect of the plurality of second filaments is a    different type of optical effect than the optical effect of the    filament.-   Aspect 105. The method of any one of the preceding aspects, further    comprising dying the SC filament, fibers comprising the SC filament,    or yarn comprising the SC filament.-   Aspect 106. The method of any one of the preceding aspects, wherein    the structurally colored thermoplastic material comprises at least    one thermoplastic polymer, optionally wherein the at least one    thermoplastic polymer includes a thermoplastic elastomer.-   Aspect 107. The method of any one of the preceding aspects, wherein    melting includes increasing a temperature of the thermoplastic    material to a first temperature at or above a melting temperature of    the thermoplastic polymer.-   Aspect 108. The method of any one of the preceding aspects, wherein    the thermoplastic material includes one or more thermoplastic    polyurethanes, thermoplastic polyethers, thermoplastic polyesters,    thermoplastic polyamides, thermoplastic polyolefins, thermoplastic    co-polymers thereof, or a combination thereof.-   Aspect 109. The method of any one of the preceding aspects, wherein    the optical element includes at least one optical layer.-   Aspect 110. The method of any one of the preceding aspects, wherein    the optical element is single layer reflector, a single layer    filter, a multilayer reflector or a multilayer filter.-   Aspect 111. The method of any one of the preceding aspects, wherein    the multilayer reflector has at least two layers, including at least    two adjacent layers having different refractive indices.-   Aspect 112. The method of any one of the preceding aspects, wherein    at least one of the layers of the multilayer reflector has a    thickness that is about one-fourth of the wavelength of visible    light.-   Aspect 113. The method of any one of the preceding aspects, wherein    at least one of the layers of the multilayer reflector comprises a    material selected from the group consisting of: silicon dioxide,    titanium dioxide, zinc sulfide, magnesium fluoride, tantalum    pentoxide, and a combination thereof.-   Aspect 114. The method of any one of the preceding aspects, further    comprising a textured surface on a first side of the optical    element.-   Aspect 115. The method of any one of the preceding aspects, wherein    the textured surface has a plurality of profile features and a    plurality of flat areas.-   Aspect 116. The method of any one of the preceding aspects, wherein    the textured surface includes a plurality of profile features and    flat planar areas, wherein the profile features extend above the    flat areas of the textured surface.-   Aspect 117. The method of any one of the preceding aspects, wherein    the dimensions of the profile features, a shape of the profile    features, a spacing among the plurality of the profile features, in    combination with the optical layer impart the structural color.-   Aspect 118. The method of any one of the preceding aspects, wherein    the spacing among the profile features reduces distortion effects of    the profile features produced from interfering with one another when    imparting the structural color of the structural colored pellet.-   Aspect 119. The method of any one of the preceding aspects, wherein    the profile features and the flat areas result in at least one    optical layer of the optical element having an undulating    topography, wherein the optical layer has a planar region between    neighboring depressions and/or elevations that is planar with the    flat planar areas of the textured surface.-   Aspect 120. The method of any one of the preceding aspects, wherein    the structural color of the structurally colored pellets has the    appearance of a single color or multiple colors.-   Aspect 121. The method of any one of the preceding aspects, wherein    the optical element exhibits a color that, when measured according    to the CIE 1976 color space under a given illumination condition at    three observation angles of about −15 to 180 degrees or about −15    degrees and +60 degrees, has a first color measurement at a first    angle of observation having coordinates L₁* and a₁* and b₁*, and a    second color measurement at a second angle of observation having    coordinates L₂* and a₂* and b₂*, and a third color measurement at a    third angle of observation having coordinates L3* and a₃* and b₃*,    wherein the L₁*, L₂*, and L₃* values may be the same or different,    wherein the a₁*, a₂*, and a₃* coordinate values may be the same or    different, wherein the b₁*, b₂*, and b₃* coordinate values may be    the same or different, and wherein the range of the combined a₁*,    a₂* and a₃* values is less than about 40% of the overall scale of    possible a* values, optionally is less than about 30% of the overall    scale of possible a* values, optionally is less than about 20% of    the overall scale of possible a* values, or optionally is less than    about 10% of the overall scale of possible a* values.-   Aspect 122. The method of any one of the preceding aspects, wherein    the optical element exhibits a color that, when measured according    to the CIE 1976 color space under a given illumination condition at    three observation angles of about −15 to 180 degrees or about −15    degrees and +60 degrees, has a first color measurement at a first    angle of observation having coordinates L₁* and a₁* and b₁*, and a    second color measurement at a second angle of observation having    coordinates L₂* and a₂* and b₂*, and a third color measurement at a    third angle of observation having coordinates L₃* and a₃* and b₃*,    wherein the L₁*, L₂*, and L3* values may be the same or different,    wherein the a₁*, a₂*, and a₃* coordinate values may be the same or    different, wherein the b₁*, b₂*, and b₃* coordinate values may be    the same or different, and wherein the range of the combined b₁*,    b₂* and b₃* values is less than about 40% of the overall scale of    possible b* values, optionally is less than about 30% of the overall    scale of possible b* values, optionally is less than about 20% of    the overall scale of possible b* values, or optionally is 10% of the    overall scale of possible b* values.-   Aspect 123. The method of any one of the preceding aspects, wherein    the optical element exhibits a color that, when measured according    to the CIE 1976 color space under a given illumination condition at    two observation angles of about −15 to 180 degrees or about −15    degrees and +60 degrees, has a first color measurement at a first    angle of observation having coordinates L₁* and a₁* and b₁*, and a    second color measurement at a second angle of observation having    coordinates L₂* and a₂* and b₂*, wherein the L₁* and L₂* values may    be the same or different, wherein the a₁* and a₂* coordinate values    may be the same or different, wherein the b₁* and b₂* coordinate    values may be the same or different, and wherein the ΔE*_(ab)    between the first color measurement and the second color measurement    is greater than or equal to about 100, where    ΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²′(b₁*−b₂*)²]^(1/2), optionally is    greater than or equal to about 80, or optionally is greater than or    equal to about 60 or alternatively less than 3, less than 2.2, or    less than 2.-   Aspect 124. The method of any one of the preceding aspects, wherein    the optical element exhibits a color that, when measured according    to the CIELCH color space under a given illumination condition at    three observation angles of about −15 to 180 degrees or about −15    degrees and +60 degrees, has a first color measurement at a first    angle of observation having coordinates L₁* and C₁* and h₁°, and a    second color measurement at a second angle of observation having    coordinates L₂* and C₂* and h₂°, and a third color measurement at a    third angle of observation having coordinates L₃* and C₃* and h₃°,    wherein the L₁*, L₂*, and L3* values may be the same or different,    wherein the C₁*, C₂*, and C₃* coordinate values may be the same or    different, wherein the h₁+, h₂° and h₃° coordinate values may be the    same or different, and wherein the range of the combined h₁°, h₂°    and h₃° values is greater than about 60 degrees, optionally is    greater than about 50 degrees, optionally is greater than about 40    degrees, optionally is greater than about 30 degrees, or optionally    is greater than about 20 degrees or alternatively less than 10    degrees or less than 5 degrees.-   Aspect 125. The method of one the preceding aspects, wherein the    structural color is visible to a viewer having 20/20 visual acuity    and normal color vision from a distance of about 1 meter from the    article.-   Aspect 126. The method of one the preceding aspects, wherein the    structural color has a single hue.-   Aspect 127. The method of one the preceding aspects, wherein the    structural color includes two or more hues.-   Aspect 128. The method of one the preceding aspects, wherein the    structural color has limited iridescence.-   Aspect 129. The method of one the preceding aspects, wherein the    structural color is not iridescence.-   Aspect 130. The method of one the preceding aspects, wherein the    structural color has limited iridescence such that, when each color    visible at each possible angle of observation is assigned to a    single hue selected from the group consisting of the primary,    secondary and tertiary colors on the red yellow blue (RYB) color    wheel, all of the assigned hues fall into a single hue group,    wherein the single hue group is one of a) green-yellow, yellow, and    yellow-orange; b) yellow, yellow-orange and orange; c)    yellow-orange, orange, and orange-red; d) orange-red, and    red-purple; e) red, red-purple, and purple; f) red-purple, purple,    and purple-blue; g) purple, purple-blue, and blue; h) purple-blue,    blue, and blue-green; i) blue, blue-green and green; and j)    blue-green, green, and green-yellow.-   Aspect 131. The method of one the preceding aspects, wherein the    structural color having limited iridescence is limited to two or    three of the hues green-yellow, yellow, yellow-orange; or the hues    purple-blue, blue, and blue-green; or the hues orange-red, red, and    red-purple; or the hues blue-green, green, and green-yellow; or the    hues yellow-orange, orange, and orange-red; or the hues red-purple,    purple, and purple-blue.-   Aspect 132. The method of one of the preceding aspects, wherein an    article comprises the SC filament.-   Aspect 133. The method of one of the preceding aspects, wherein the    article or substrate is an article of footwear, an article of    apparel, or an article of sporting equipment.-   Aspect 134. A method of forming structurally colored item,    comprising:

disposing an optical element onto a pellet for form a structurallycolored pellet, wherein the optical element imparts an optical effect tothe structurally colored pellets.

-   Aspect 135. The method of any one of the preceding aspects, wherein    the optical effect is a structural color and not iridescent or    metallic.-   Aspect 136. The method of any one of the preceding aspects, wherein    the optical effect is an iridescent appearance.-   Aspect 137. The method of any one of the preceding aspects, wherein    the optical effect is a metallic appearance.-   Aspect 138. The method of any one of the preceding aspects, wherein    the optical effect imparts two or more different hues to the    filament when the filament is viewed from at least two different    angles 15 degrees apart.-   Aspect 139. The method of any one of the preceding aspects, wherein    the optical effect imparted to the filament is visible to a viewer    having 20/20 visual acuity and normal color vision from a distance    of about 1 meter from the article.-   Aspect 140. The method of any one of the preceding aspects, wherein    the structurally colored item is a SC filament.-   Aspect 141. The method of any one of the preceding aspects, further    comprising forming a fiber or a yarn, wherein the fiber or yarn    comprises the SC filament.-   Aspect 142. The method of any one of the preceding aspects, wherein    the yarn is a monofilament yarn or a multi-filament yarn.-   Aspect 143. The method of any one of the preceding aspects, wherein    the yarn is a staple yarn including a plurality of staple fibers    formed by cutting or chopping the SC filament.-   Aspect 144. The method of any one of the preceding aspects, wherein    the SC filament is present in a staple yarn, a monofilament yarn, or    a multifilament yarn; optionally wherein the yarn has a tenacity of    about 1.5 grams per Denier to about 4.0 grams per Denier; or has    tenacity of greater than 4.0 grams per Denier; or has a tenacity of    about 5.0 grams per Denier to about 10 grams per Denier.-   Aspect 145. The method of any one of the preceding aspects, wherein    the SC filament of a staple fiber has an aspect ratio of 10 to    100,000.-   Aspect 146. The method of any one of the preceding aspects, wherein    the SC filament is present in the form of a textile, and optionally    wherein the textile is a non-woven textile, a woven textile, a knit    textile, a braided textile, or a crocheted textile.-   Aspect 147. The method of any one of the preceding aspects, wherein    the SC filament is attached to a substrate, optionally wherein the    SC filament is stitched to or embroidered to the substrate.-   Aspect 148. The method of any one of the preceding aspects, wherein    the SC filament is included with a plurality of second filaments in    the form of a tow.-   Aspect 149. The method of any one of the preceding aspects, wherein    the plurality of second filaments of the tow are substantially free    of optical elements.-   Aspect 150. The method of any one of the preceding aspects, wherein    the plurality of second filaments of the tow comprise second optical    elements imparting a second optical effect to the second filaments.-   Aspect 151. The method of any one of the preceding aspects, wherein    the second optical effect of the plurality of second filaments is a    different type of optical effect than the optical effect of the    filament.-   Aspect 152. The method of any one of the preceding aspects, further    comprising dying the SC filament, fibers comprising the filament, or    yarn comprising the SC filament.-   Aspect 153. The method of any one of the preceding aspects, wherein    the features described in aspects 41-68 also describe features of    aspects 134-153.-   Aspect 154. The article and/or method of any of the preceding    aspects, wherein the profile feature has at least one dimension    greater than 500 micrometers and optionally greater than about 600    micrometers.-   Aspect 155. The article and/or method of any of the preceding    aspects, wherein at least one of the length and width of the profile    feature is greater than 500 micrometers or optionally both the    length and the width of the profile feature is greater than 500    micrometers.-   Aspect 156. The article and/or method of any of the preceding    aspects, wherein the height of the profile features can be greater    than 50 micrometers or optionally greater than about 60 micrometers.-   Aspect 157. The article and/or method of any of the preceding    aspects, wherein at least one of the length and width of the profile    feature is less than 500 micrometers or both the length and the    width of the profile feature is less than 500 micrometers, while the    height is greater than 50 micrometers.-   Aspect 158. The article and/or method of any of the preceding    aspects, wherein at least one of the length and width of the profile    feature is greater than 500 micrometers or both the length and the    width of the profile feature is greater than 500 micrometers, while    the height is greater than 50 micrometers.-   Aspect 159. The article and/or method of any of the preceding    aspects, wherein at least one of the dimensions of the profile    feature is in the nanometer range, while at least one other    dimension is in the micrometer range.-   Aspect 160. The article and/or method of any of the preceding    aspects, wherein the nanometer range is about 10 nanometers to about    1000 nanometers, while the micrometer range is about 5 micrometers    to 500 micrometers.-   Aspect 161. The article and/or method of any of the preceding    aspects, wherein at least one of the length and width of the profile    feature is in the nanometer range, while the other of the length and    the width of the profile feature is in the micrometer range.-   Aspect 162. The article and/or method of any of the preceding    aspects, wherein height of the profile features is greater than 250    nanometers.-   Aspect 163. The article and/or method of any of the preceding    aspects, wherein at least one of the length and width of the profile    feature is in the nanometer range and the other in the micrometer    range, where the height is greater than 250 nanometers.-   Aspect 164. The article and/or method of any of the preceding    aspects, wherein spatial orientation of the profile features is    periodic.-   Aspect 165. The article and/or method of any of the preceding    aspects, wherein spatial orientation of the profile features is a    semi-random pattern or a set pattern.-   Aspect 166. The article and/or method of any of the preceding    aspects, wherein the surface of the layers of the inorganic optical    element are a substantially three-dimensional flat planar surface or    a three-dimensional flat planar surface.

Now having described embodiments of the present disclosure generally,additional discussion regarding embodiments will be described in greaterdetails.

This disclosure is not limited to particular embodiments described, andas such may, of course, vary. The terminology used herein serves thepurpose of describing particular embodiments only, and is not intendedto be limiting, since the scope of the present disclosure will belimited only by the appended claims.

Where a range of values is provided, each intervening value, to thetenth of the unit of the lower limit unless the context clearly dictatesotherwise, between the upper and lower limit of that range and any otherstated or intervening value in that stated range, is encompassed withinthe disclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges and are also encompassedwithin the disclosure, subject to any specifically excluded limit in thestated range. Where the stated range includes one or both of the limits,ranges excluding either or both of those included limits are alsoincluded in the disclosure.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features which may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentdisclosure. Any recited method may be carried out in the order of eventsrecited or in any other order that is logically possible.

Embodiments of the present disclosure will employ, unless otherwiseindicated, techniques of material science, chemistry, textiles, polymerchemistry, and the like, which are within the skill of the art. Suchtechniques are explained fully in the literature.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art of material science, chemistry, textiles, polymer chemistry, andthe like. Although methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of the presentdisclosure, suitable methods and materials are described herein.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” may include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “a support”includes a plurality of supports. In this specification and in theclaims that follow, reference will be made to a number of terms thatshall be defined to have the following meanings unless a contraryintention is apparent.

The present disclosure provides for SC filaments and methods of makingSC filaments. The SC filament can include a plurality of opticalelements that impart an optical effect such as a color, a metallicappearance, or an iridescent appearance as a result of structural coloreffects. The optical elements or fragments of the optical elements arerandomly dispersed throughout and on the surface of the SC filament sothat the optical effect is imparted to the SC filament to produce anaesthetically appealing appearance. The optical effect can be donewithout requiring the use of inks or pigments and the environmentalimpact associated with their use, while in other situations ink and/orpigments can be used in combination with the optical elements orfragments thereof. Scattering, refraction, reflection, interference,and/or diffraction of visible wavelengths of light by the opticalelements and/or fragments thereof can produce the optical effect such asstructural color (e.g., hues of blue, green, red, yellow, and the like),where two types of the structural color can be the iridescent ormetallic appearance.

The SC filament can be included in yarns and fibers. The SC filaments,fibers, and yarns can be included in a textile. A “textile” may bedefined as any material manufactured from fibers, filaments, or yarns(e.g., SC or other type) characterized by flexibility, fineness, and ahigh ratio of length to thickness. Textiles generally fall into twocategories. The first category includes textiles produced directly fromwebs of filaments (e.g., SC or other type) or fibers (e.g., SC filamentbased or other type) by randomly interlocking to construct non-wovenfabrics and felts. The second category includes textiles formed througha mechanical manipulation of yarn (e.g., SC filament based or othertype), thereby producing a woven fabric, a knitted fabric, a braidedfabric, a crocheted fabric, and the like (e.g., including the SCfilament). The yarns, fibers, and articles of manufacture can includeone or more SC filaments (the same or different types of SC filaments)as well as other types of filaments, fibers, and yarns. For simplicity,each reference to fiber, yarn, and article of manufacture may not listthat it includes a SC filament and it will be understood that eachreference to fiber, yarn, and article of manufacture can include one ormore SC filaments even if that is not expressly stated unless it isotherwise evident that a SC filament is intended to be excluded.

The terms “filament,” “fiber,” or “fibers” refer to materials that arein the form of discrete elongated pieces that are significantly longerthan they are wide. The fibers can have an indefinite length and can becut to form staple SC fibers of relatively uniform length. The SC staplefiber can have a have a length of about 1 millimeter to 100 centimetersor more as well as any increment therein (e.g., 1 millimeterincrements). The SC fiber can have any of a variety of cross-sectionalshapes similar to those described in connection with other fibersdescribed herein. In some cases a fiber can be a multi-component fiber,such as one comprising two or more co-extruded polymeric materials(e.g., one including the optical elements or fragments thereof). Aplurality of SC fibers includes 2 to hundreds or thousands or more SCfibers (the same or different types) or other types of fibers. Theplurality of fibers can be in the form of bundles of strands of fibers,referred to as tows, or in the form of relatively aligned staple fibersreferred to as sliver and roving. As used herein, the term “yarn” refersto an assembly formed of one or more SC fibers (the same or differenttypes) or other types of fibers, wherein the strand has a substantiallength and a relatively small cross-section, and is suitable for use inthe production of textiles by hand or by machine, including textilesmade using weaving, knitting, crocheting, braiding, sewing, embroidery,or ropemaking techniques. Thread is a type of yarn commonly used forsewing. Two or more yarns can be combined, for example, to formcomposite yarns such as single- or double-covered yarns, and corespunyarns. Accordingly, yarns may have a variety of configurations thatgenerally conform to the descriptions provided herein.

Various techniques exist for mechanically manipulating yarns to form atextile. Such techniques include, for example, interweaving,intertwining and twisting, and interlooping. Interweaving is theintersection of two yarns that cross and interweave at right angles toeach other. The textile can be a nonwoven textile. Generally, a nonwoventextile or fabric is a sheet or web structure made from fibers and/oryarns that are bonded together. Additional details regarding filaments,fibers, and yarns is provided below.

The SC filaments and yarns or fibers thereof can be incorporated intoarticles of manufacture such as an article of footwear, an article ofapparel, or an article of sporting equipment or components of any ofthese. The article of manufacture can include footwear, apparel (e.g.,shirts, jerseys, pants, shorts, gloves, glasses, socks, hats, caps,jackets, undergarments), containers (e.g., backpacks, bags), andupholstery for furniture (e.g., chairs, couches, car seats), bedcoverings (e.g., sheets, blankets), table coverings, towels, flags,tents, sails, and parachutes, or components of any one of these. Inaddition, the component including the SC filaments and yarns or fibersthereof can be used with or disposed on textiles or other items such asstriking devices (e.g., bats, rackets, sticks, mallets, golf clubs,paddles, etc.), athletic equipment (e.g., golf bags, baseball andfootball gloves, soccer ball restriction structures), protectiveequipment (e.g., pads, helmets, guards, visors, masks, goggles, etc.),locomotive equipment (e.g., bicycles, motorcycles, skateboards, cars,trucks, boats, surfboards, skis, snowboards, etc.), balls or pucks foruse in various sports, fishing or hunting equipment, furniture,electronic equipment, construction materials, eyewear, timepieces,jewelry, and the like.

The article can be an article of footwear. The article of footwear canbe designed for a variety of uses, such as sporting, athletic, military,work-related, recreational, or casual use. Primarily, the article offootwear is intended for outdoor use on unpaved surfaces (in part or inwhole), such as on a ground surface including one or more of grass,turf, gravel, sand, dirt, clay, mud, pavement, and the like, whether asan athletic performance surface or as a general outdoor surface.However, the article of footwear may also be desirable for indoorapplications, such as indoor sports including dirt playing surfaces forexample (e.g., indoor baseball fields with dirt infields).

The article of footwear can be designed for use in indoor or outdoorsporting activities, such as global football/soccer, golf, Americanfootball, rugby, baseball, running, track and field, cycling (e.g., roadcycling and mountain biking), and the like. The article of footwear canoptionally include traction elements (e.g., lugs, cleats, studs, andspikes as well as tread patterns) to provide traction on soft andslippery surfaces, where articles of the present disclosure can be usedor applied between or among the traction elements and optionally on thesides of the traction elements but on the surface of the tractionelement that contacts the ground or surface. Cleats, studs and spikesare commonly included in footwear designed for use in sports such asglobal football/soccer, golf, American football, rugby, baseball, andthe like, which are frequently played on unpaved surfaces. Lugs and/orexaggerated tread patterns are commonly included in footwear includingboots design for use under rugged outdoor conditions, such as trailrunning, hiking, and military use.

The article can be an article of apparel (i.e., a garment). The articleof apparel can be an article of apparel designed for athletic or leisureactivities. The article of apparel can be an article of apparel designedto provide protection from the elements (e.g., wind and/or rain), orfrom impacts.

The article can be an article of sporting equipment. The article ofsporting equipment can be designed for use in indoor or outdoor sportingactivities, such as global football/soccer, golf, American football,rugby, baseball, running, track and field, cycling (e.g., road cyclingand mountain biking), and the like.

FIGS. 1A-M illustrate articles of manufacture that include the SCfilaments or fibers and/or yarns thereof of the present disclosure. TheSC filaments and fibers or and/or yarns thereof are represented byhashed areas 12A′/12M′-12A″/12M″. The location of the SC filaments andfibers or and/or yarns thereof are provided only to indicate onepossible area that the SC filaments or fibers or and/or yarns thereofcan be located. Also, two locations are illustrated in the figures, butthis is done only for illustration purposes as the articles can includeone or a plurality of areas for the SC filaments and fibers or and/oryarns thereof, where the size and location can be determined based onthe article of manufacture. The SC filaments or fibers and/or yarnsthereof located on each article of manufacture can represent a number,letter, symbol, design, emblem, graphic mark, icon, logo, or the like.

FIGS. 1N(a) and 1N(b) illustrate a perspective view and a side view ofan article of footwear 100 that include a sole structure 104 and anupper 102. The structure including the SC filaments or fibers and/oryarns thereof is represented by 122 a and 122 b. The sole structure 104is secured to the upper 102 and extends between the foot and the groundwhen the article of footwear 100 is worn. The primary elements of thesole structure 104 are a midsole 114 and an outsole 112. The midsole 114is secured to a lower area of the upper 102 and may be formed of apolymer foam or another appropriate material. In other configurations,the midsole 114 can incorporate fluid-filled chambers, plates,moderators, and/or other elements that further attenuate forces, enhancestability, or influence motions of the foot. The outsole 112 is securedto a lower surface of the midsole 114 and may be formed from awear-resistant rubber material that is textured to impart traction, forexample. The upper 102 can be formed from various elements (e.g., lace,tongue, collar) that combine to provide a structure for securely andcomfortably receiving a foot. Although the configuration of the upper102 may vary significantly, the various elements generally define a voidwithin the upper 102 for receiving and securing the foot relative tosole structure 104. Surfaces of the void within upper 102 are shaped toaccommodate the foot and can extend over the instep and toe areas of thefoot, along the medial and lateral sides of the foot, under the foot,and around the heel area of the foot. The upper 102 can be made of oneor more materials such as textiles, a polymer foam, leather, syntheticleather, and the like that are stitched or bonded together. Althoughthis configuration for the sole structure 104 and the upper 102 providesan example of a sole structure that may be used in connection with anupper, a variety of other conventional or nonconventional configurationsfor the sole structure 104 and/or the upper 102 can also be utilized,Accordingly, the configuration and features of the sole structure 104and/or the upper 102 can vary considerably.

FIGS. 1O(a) and 1O(b) illustrate a perspective view and a side view ofan article of footwear 130 that include a sole structure 134 and anupper 132. The structure including the SC filaments or fibers and/oryarns thereof is represented by 136 a and 136 b/136 b′. The solestructure 134 is secured to the upper 132 and extends between the footand the ground when the article of footwear 130 is worn. The upper 132can be formed from various elements (e.g., lace, tongue, collar) thatcombine to provide a structure for securely and comfortably receiving afoot, Although the configuration of the upper 132 may varysignificantly, the various elements generally define a void within theupper 132 for receiving and securing the foot relative to the solestructure 134. Surfaces of the void within the upper 132 are shaped toaccommodate the foot and can extend over the instep and toe areas of thefoot, along the medial and lateral sides of the foot, under the foot,and around the heel area of the foot. The upper 132 can be made of oneor more materials such as textiles including natural and syntheticleathers, molded polymeric components, polymer foam and the like thatare stitched or bonded together.

The primary elements of the sole structure 134 are a forefoot component142, a heel component 144, and an outsole 146. Each of the forefootcomponent 142 and the heel component 144 are directly or indirectlysecured to a lower area of the upper 132 and formed from a polymermaterial that encloses a fluid, which may be a gas, liquid, or gel.During walking and running, for example, the forefoot component 142 andthe heel component 144 compress between the foot and the ground, therebyattenuating ground reaction forces. That is, the forefoot component 142and the heel component 144 are inflated and may be pressurized with thefluid to cushion the foot. The outsole 146 is secured to lower areas ofthe forefoot component 142 and the heel component 144 and may be formedfrom a wear-resistant rubber material that is textured to imparttraction. The forefoot component 142 can be made of one or more polymers(e.g., layers of one or more polymers films) that form a plurality ofchambers that includes a fluid such as a gas. The plurality of chamberscan be independent or fluidic-ally interconnected. Similarly, the heelcomponent 144 can be made of one or more polymers (e.g., layers of oneor more polymers films) that form a plurality of chambers that includesa fluid such as a gas and can also be independent or fluidicallyinterconnected. In some configurations, the sole structure 134 mayinclude a foam layer, for example, that extends between the upper 132and one or both of the forefoot component 142 and the heel component144, or a foam element may be located within indentations in the lowerareas of the forefoot component 142 and the heel component 144. In otherconfigurations, the sole structure 132 may incorporate plates,moderators, lasting elements, or motion control members that furtherattenuate forces, enhance stability, or influence the motions of thefoot, for example. Although the depicted configuration for the solestructure 134 and the upper 132 provides an example of a sole structurethat may be used in connection with an upper, a variety of otherconventional or nonconventional configurations for the sole structure134 and/or the upper 132 can also be utilized. Accordingly, theconfiguration and features of the sole structure 134 and/or the upper132 can vary considerably.

FIG. 1O(c) is a cross-sectional view of A-A that depicts the upper 132and the heel component 144. The SC filaments or fibers and/or yarnsthereof 136 b can be disposed on the outside wall of the heel component144 or alternatively or optionally the SC filaments or fibers and/oryarns thereof 136 b′ can be disposed on the inside wall of the heelcomponent 144.

FIGS. 1P(a) and 1P(b) illustrate a perspective view and a side view ofan article of footwear 160 that includes traction elements 168. Thestructure including the SC filaments or fibers and/or yarns thereof isrepresented by 172 a and 172 b. The article of footwear 160 includes anupper 162 and a sole structure 164, where the upper 162 is secured tothe sole structure 164. The sole structure 164 can include one or moreof a toe plate 166 a, a mid-plate 166 b, and a heel plate 166 c. Theplate can include one or more traction elements 168, or the tractionelements can be applied directly to a ground-facing surface of thearticle of footwear. As shown in FIGS. 1P(a) and (b), the tractionelements 168 are cleats, but the traction elements can include lugs,cleats, studs, and spikes as well as tread patterns to provide tractionon soft and slippery surfaces. In general, the cleats, studs and spikesare commonly included in footwear designed for use in sports such asglobal football/soccer, golf, American football, rugby, baseball, andthe like, while lugs and/or exaggerated tread patterns are commonlyincluded in footwear (not shown) including boots design for use underrugged outdoor conditions, such as trail running, hiking, and militaryuse. The sole structure 164 is secured to the upper 162 and extendsbetween the foot and the ground when the article of footwear 160 isworn. The upper 162 can be formed from various elements (e.g., lace,tongue, collar) that combine to provide a structure for securely andcomfortably receiving a foot. Although the configuration of the upper162 may vary significantly, the various elements generally define a voidwithin the upper 162 for receiving and securing the foot relative to thesole structure 164. Surfaces of the void within upper 162 are shaped toaccommodate the foot and extend over the instep and toe areas of thefoot, along the medal and lateral sides of the foot, under the foot, andaround the heel area of the foot. The upper 162 can be made of one ormore materials such as textiles including natural and synthetic;leathers, molded polymeric; components, a polymer foam, and the likethat are stitched or bonded together. In other aspects not depicted, thesole structure 164 may incorporate foam, one or more fluid-filledchambers, plates, moderators, or other elements that further attenuateforces, enhance stability, or influence the motions of the foot.Although the depicted configuration for the sole structure 164 and theupper 162 provides an example of a sole structure that may be used inconnection with an upper, a variety of other conventional ornonconventional configurations for the sole structure 164 and/or theupper 162 can also be utilized. Accordingly, the configuration andfeatures of the sole structure 164 and/or the upper 162 can varyconsiderably.

SC filaments or fibers and/or yarns thereof and articles of manufacturemade thereof of the present disclosure include the optical element orfragments of the optical element, where each can have the characteristicof imparting optical effects including structural color (e.g., singlecolor, multicolor, iridescent, metallic). The optical element caninclude at least one optical layer (e.g., a single layer reflector, asingle layer filter, a multilayer reflector or a multilayer filter)optionally having a textured surface (e.g., integral to the opticalelement or as part of the surface of the article), optionally with aprotective layer, or optionally with any combination of the texturedsurface and the protective layer. Optical elements or fragments of theoptical element on the surface of the filaments cause the articlefilament, fiber, yarn, or article of manufacture to appear to be colored(i.e., to have a new, different color (e.g., a color which differs inhue or iridescence or as otherwise described herein) than the color thesurface of the article without the optical element or fragments thereof)without the application of additional pigments or dyes to the article.However, pigments and/or dyes can be used in conjunction with theoptical element to produce aesthetically pleasing effects.

The SC filament can be produced by melting a plurality of structurallycolored articles and then extruding the molten material to form the SCfilament. Melting can be accomplished by bringing the structurallycolored articles to a temperature and/or pressure to cause the materialto melt, for example to a temperature at or above the melting point ofthe material (e.g., thermoplastic polymer). Extruding can beaccomplished using an extruder such as a single screw or multi-screwextruder. The structurally colored article can include a thermoplasticmaterial and a plurality of the optical elements. The structurallycolored article can include pellets, films, sheets, and articles as wellas extruded versions of each, where each has one or more opticalelements. Depending upon how the structurally colored articles areproduced and/or processing of the structurally color article (e.g., theextrusion process), the SC filament can include intact optical elementsas originally produced and/or fragments of the optical elements. Despitebeing processed (e.g., extruding, grinding, cutting, shredding,crushing, or a combination thereof), a portion of the optical elementsand/or the fragments of the optical elements are not deteriorated andcan impart the optical effect to the filament. Another portion of theoptical elements and/or the fragments thereof are deteriorated andcannot impart the optical effect to the filament.

The plurality of optical elements and the fragments thereof can make upat least 1 percent by weight, or at least 2 percent by weight, or atleast 5 percent by weight, or at least 7 percent by weight, or at least10 percent by weight of a total weight of the filament.

The structurally colored articles can be formed by disposing (e.g.,affixing, attaching, adhering, bonding, joining) the optical elementdirectly onto an article in a manner as described herein. Alternatively,the structurally colored articles can be formed by processing (e.g.,grinding, cutting, shredding, crushing, extruding, or a combinationthereof) a polymer-based item that includes a thermoplastic material andat least one optical element. The polymer-based item can includepellets, films, sheets, and articles, each having the optical structure.During the processing of the polymer-based item, a portion of theoptical elements are unchanged while another portion of the opticalelements form fragments thereof, where all or some of the opticalelements or fragments of the optical elements retain the characteristicto impart the optical effect. The pieces of the polymer-based itemformed from the processing can be melted to form a molten material,which can then be extruded to form the structurally colored articles.The optical elements and/or fragments of one or more optical elementsfrom the processing step can also form other fragments of one or moreoptical elements during the extrusion process. The optical elementand/or fragments of optical element impart the optical effect to thestructurally colored articles. The optical effect before and afterprocessing and/or extrusion may be the same or different. For example,prior to one or more of the processing steps, the optical effect astructure color of blue and after processing the optical effect impartis iridescent appearance or metallic appearance.

The optical element on the structurally colored article can be astructurally colored coating covering at least 25 percent, or at least50 percent, or at least 75 percent of a total surface area of thestructurally colored article.

As has been described herein, the structural color can include one of anumber of colors. The “color” of SC filaments or fibers and/or yarnsthereof and article of manufacture as perceived by a viewer can differfrom the actual color of the article, as the color perceived by a vieweris determined by the actual color of the article by the presence ofoptical elements which may absorb, refract, interfere with, or otherwisealter light reflected by the article, by the viewer's ability to detectthe wavelengths of light reflected by the article, by the wavelengths oflight used to illuminate the article, as well as other factors such asthe coloration of the environment of the article, and the type ofincident light (e.g., sunlight, fluorescent light, and the like). As aresult, the color of an object as perceived by a viewer can differ fromthe actual color of the article.

Conventionally, color is imparted to man-made objects by applyingcolored pigments or dyes to the object. More recently, methods ofimparting “structural color” to man-made objects have been developed.Structural color is color which is produced, at least in part, bymicroscopically structured surfaces that interfere with visible lightcontacting the surface. The structural color is color caused by physicalphenomena including the scattering, refraction, reflection,interference, and/or diffraction of light, unlike color caused by theabsorption or emission of visible light through coloring matters. Forexample, optical phenomena which impart structural color can includemultilayer interference, thin-film interference, refraction, dispersion,light scattering, Mie scattering, diffraction, and diffraction grating.In various aspects described herein, structural color imparted to anarticle can be visible to a viewer having 20/20 visual acuity and normalcolor vision from a distance of about 1 meter from the article. Inaddition to “colors”, the structural color can be iridescent ormetallic.

As described herein, structural color is produced, at least in part, bythe optical element, as opposed to the color being produced solely bypigments and/or dyes. The coloration of a structurally-colored article(e.g., the SC filament or fiber or an article including the SCfilament(s) or fiber(s)) can be due solely to structural color (i.e.,the article, a colored portion of the article, or a colored outer layerof the article can be substantially free of pigments and/or dyes).Structural color can also be used in combination with pigments and/ordyes, for example, to alter all or a portion of a structural color.

“Hue” is commonly used to describe the property of color which isdiscernible based on a dominant wavelength of visible light, and isoften described using terms such as magenta, red, orange, yellow, green,cyan, blue, indigo, violet, etc. or can be described in relation (e.g.,as similar or dissimilar) to one of these. The hue of a color isgenerally considered to be independent of the intensity or lightness ofthe color. For example, in the Munsell color system, the properties ofcolor include hue, value (lightness) and chroma (color purity).Particular hues are commonly associated with particular ranges ofwavelengths in the visible spectrum: wavelengths in the range of about700 to 635 nanometers are associated with red, the range of about 635 to590 nanometers is associated with orange, the range of about 590 to 560nanometers is associated with yellow, the range of about 560 to 520nanometers is associated with green, the range of about 520 to 490nanometers is associated with cyan, the range of about 490 nanometers to450 nanometers is associated with blue, and the range of about 450 to400 nanometers is associated with violet.

The color (including the hue) of an article as perceived by a viewer candiffer from the actual color of the article. The color as perceived by aviewer depends not only on the physics of the article, but also itsenvironment, and the characteristics of the perceiving eye and brain.For example, as the color perceived by a viewer is determined by theactual color of the article (e.g., the color of the light leaving thesurface of the article), by the viewer's ability to detect thewavelengths of light reflected or emitted by the article, by thewavelengths of light used to illuminate the article, as well as otherfactors such as the coloration of the environment of the article, andthe type of incident light (e.g., sunlight, fluorescent light, and thelike). As a result, the color of an object as perceived by a viewer candiffer from the actual color of the article.

When used in the context of structural color, one can characterize thehue of a structurally-colored article, i.e., an article that has beenstructurally colored by incorporating an optical element or fragmentsthereof into the article, based on the wavelengths of light thestructurally-colored portion of the article absorbs and reflects (e.g.,linearly and non-linearly). While the optical element or fragmentsthereof may impart a first structural color, the presence of an optionaltextured surface can alter the structural color. Other factors such ascoatings or transparent elements may further alter the perceivedstructural color. The hue of the structurally colored article caninclude any of the hues described herein as well as any other hues orcombination of hues. The structural color can be referred to as a“single hue” (i.e., the hue remains substantially the same, regardlessof the angle of observation and/or illumination), or “multihued” (i.e.,the hue varies depending upon the angle of observation and/orillumination). The multihued structural color can be iridescent (i.e.,the hue changes gradually over two or more hues as the angle ofobservation or illumination changes). The hue of an iridescent multihuedstructural color can change gradually across all the hues in the visiblespectrum (e.g., like a “rainbow”) as the angle of observation orillumination changes. The hue of an iridescent multihued structuralcolor can change gradually across a limited number of hues in thevisible spectrum as the angle of observation or illumination changes, inother words, one or more hues in the visible spectrum (e.g., red,orange, yellow, etc.) are not observed in the structural color as theangle of observation or illumination changes. Only one hue, orsubstantially one hue, in the visible spectrum may be present for asingle-hued structural color. The hue of a multihued structural colorcan change more abruptly between a limited number of hues (e.g., between2-8 hues, or between 2-4 hues, or between 2 hues) as the angle ofobservation or illumination changes.

The structural color can be a multi-hued structural color in which twoor more hues are imparted by the structural color.

The structural color can be iridescent multi-hued structural color inwhich the hue of the structural color varies over a wide number of hues(e.g., 4, 5, 6, 7, 8 or more hues) when viewed at a single viewingangle, or when viewed from two or more different viewing angles that areat least 15 degrees apart from each other.

The structural color can be limited iridescent multi-hue structuralcolor in which the hue of the structural color varies, or variessubstantially (e.g., about 90 percent, about 95 percent, or about 99percent) over a limited number of hues (e.g., 2 hues, or 3 hues) whenviewed from two or more different viewing angles that are at least 15degrees apart from each other. In some aspects, a structural colorhaving limited iridescence is limited to two, three or four huesselected from the RYB primary colors of red, yellow and blue, optionallythe RYB primary and secondary colors of red, yellow, blue, green, orangeand purple, or optionally the RYB primary, secondary and tertiary colorsof red, yellow, blue, green, orange purple, green-yellow, yellow-orange,orange-red, red-purple, purple-blue, and blue-green.

The structural color can be single-hue angle-independent structuralcolor in which the hue, the hue and value, or the hue, value and chromaof the structural color is independent of or substantially (e.g., about90 percent, about 95 percent, or about 99 percent) independent of theangle of observation. For example, the single-hue angle-independentstructural color can display the same hue or substantially the same huewhen viewed from at least 3 different angles that are at least 15degrees apart from each other (e.g., single-hue structural color).

The structural color imparted can be a structural color having limitediridescence such that, when each color observed at each possible angleof observation is assigned to a single hue selected from the groupconsisting of the primary, secondary and tertiary colors on the redyellow blue (RYB) color wheel, for a single structural color, all of theassigned hues fall into a single hue group, wherein the single hue groupis one of a) green-yellow, yellow, and yellow-orange; b) yellow,yellow-orange and orange; c) yellow-orange, orange, and orange-red; d)orange-red, and red-purple; e) red, red-purple, and purple; f)red-purple, purple, and purple-blue; g) purple, purple-blue, and blue;h) purple-blue, blue, and blue-green; i) blue, blue-green and green; andj) blue-green, green, and green-yellow. In other words, in this exampleof limited iridescence, the hue (or the hue and the value, or the hue,value and chroma) imparted by the structural color varies depending uponthe angle at which the structural color is observed, but the hues ofeach of the different colors viewed at the various angles ofobservations varies over a limited number of possible hues. The huevisible at each angle of observation can be assigned to a singleprimary, secondary or tertiary hue on the red yellow blue (RYB) colorwheel (i.e., the group of hues consisting of red, yellow, blue, green,orange purple, green-yellow, yellow-orange, orange-red, red-purple,purple-blue, and blue-green). For example, while a plurality ofdifferent colors are observed as the angle of observation is shifted,when each observed hue is classified as one of red, yellow, blue, green,orange purple, green-yellow, yellow-orange, orange-red, red-purple,purple-blue, and blue-green, the list of assigned hues includes no morethan one, two, or three hues selected from the list of RYB primary,secondary and tertiary hues. In some examples of limited iridescence,all of the assigned hues fall into a single hue group selected from huegroups a)-j), each of which include three adjacent hues on the RYBprimary, secondary and tertiary color wheel. For example, all of theassigned hues can be a single hue within hue group h) (e.g., blue), orsome of the assigned hues can represent two hues in hue group h) (e.g.,purple-blue and blue), or can represent three hues in hue group h)(e.g., purple-blue, blue, and blue-green).

Similarly, other properties of the structural color, such as thelightness of the color, the saturation of the color, and the purity ofthe color, among others, can be substantially the same regardless of theangle of observation or illumination, or can vary depending upon theangle of observation or illumination. The structural color can have amatte appearance, a glossy appearance, or a metallic appearance, or acombination thereof.

As discussed above, the color (including hue) of a structurally-coloredarticle can vary depending upon the angle at which thestructurally-colored article is observed or illuminated. The hue or huesof an article can be determined by observing the article, orilluminating the article, at a variety of angles using constant lightingconditions. As used herein, the “angle” of illumination or viewing isthe angle measured from an axis or plane that is orthogonal to thesurface. The viewing or illuminating angles can be set between about 0and 180 degrees. The viewing or illuminating angles can be set at 0degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and -15 degreesand the color can be measured using a colorimeter or spectrophotometer(e.g., Konica Minolta), which focuses on a particular area of thearticle to measure the color. The viewing or illuminating angles can beset at 0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, 75degrees, 90 degrees, 105 degrees, 120 degrees, 135 degrees, 150 degrees,165 degrees, 180 degrees, 195 degrees, 210 degrees, 225 degrees, 240degrees, 255 degrees, 270 degrees, 285 degrees, 300 degrees, 315degrees, 330 degrees, and 345 degrees and the color can be measuredusing a colorimeter or spectrophotometer. In a particular example of amultihued article colored using only structural color, when measured at0 degrees, 15 degrees, 30 degrees, 45 degrees, 60 degrees, and −15degrees, the hues measured for article consisted of “blue” at three ofthe measurement angles, “blue-green” at 2 of the measurement angles and“purple” at one of the measurement angles.

In other embodiments, the color (including hue, value and/or chroma) ofa structurally-colored article does not change substantially, if at all,depending upon the angle at which the article is observed orilluminated. In instances such as this the structural color can be anangle-independent structural color in that the hue, the hue and value,or the hue, value and chroma observed is substantially independent or isindependent of the angle of observation.

Various methodologies for defining color coordinate systems exist. Oneexample is L*a*b* color space, where, for a given illuminationcondition, L* is a value for lightness, and a* and b* are values forcolor-opponent dimensions based on the CIE coordinates (CIE 1976 colorspace or CIELAB). In an embodiment, a structurally-colored articlehaving structural color can be considered as having a “single” colorwhen the change in color measured for the article is within about 10% orwithin about 5% of the total scale of the a* or b* coordinate of theL*a*b* scale (CIE 1976 color space) at three or more measuredobservation or illumination angles selected from measured at observationor illumination angles of 0 degrees, 15 degrees, 30 degrees, 45 degrees,60 degrees, and −15 degrees. In certain embodiments, colors which, whenmeasured and assigned values in the L*a*b* system that differ by atleast 5 percent of the scale of the a* and b* coordinates, or by atleast 10 percent of the scale of the a* and b* coordinates, areconsidered to be different colors. The structurally-colored article canhave a change of less than about 40%, or less than about 30%, or lessthan about 20%, or less than about 10%, of the total scale of the a*coordinate or b* coordinate of the L*a*b* scale (CIE 1976 color space)at three or more measured observation or illumination angles.

A change in color between two measurements in the CIELAB space can bedetermined mathematically. For example, a first measurement hascoordinates L₁*, a₁* and b₁*, and a second measurement has coordinatesL₂*, a₂* and b₂*. The total difference between these two measurements onthe CIELAB scale can be expressed as ΔE*_(ab), which is calculated asfollows: ΔE*_(ab)=[(L₁*−L₂*)²+(a₁*−a₂*)²+(b₁*−b₂*)²]^(1/2). Generallyspeaking, if two colors have a ΔE*_(ab) of less than or equal to 1, thedifference in color is not perceptible to human eyes, and if two colorshave a ΔE*_(ab) of greater than 100 the colors are considered to beopposite colors, while Δa E*_(ab) of about 2-3 is considered thethreshold for perceivable color difference. In certain embodiments, astructurally colored article having structural color can be consideredas having a two colors when the ΔE*_(ab) of about 3 to 60, or about 3 to50, or about 3 to 40, or about 3 to 30, between three or more measuredobservation or illumination angles selected from measured at observationor illumination angles of 0 degrees, 15 degrees, 30 degrees, 45 degrees,60 degrees, and -15 degrees. The structurally-colored article can have aΔE*_(ab) that is about 3 to about 100, or about 3 to about 80, or about3 to about 60, between two or more measured observation or illuminationangles. In certain embodiments, a structurally colored article havingstructural color can be considered as having a single color when theΔE*_(ab) of about 1 to 3, or about 1 to 2.5, or about 1 to 2.2, betweenthree or more measured observation or illumination angles selected frommeasured at observation or illumination angles of 0 degrees, 15 degrees,30 degrees, 45 degrees, 60 degrees, and -15 degrees. In certainembodiments, a structurally colored article having structural color canbe considered as having a single color when the ΔE*_(ab) of about 1 to3, or about 1 to 2.5, or about 1 to 2.2, between two or more measuredobservation or illumination angles selected from measured at observationor illumination angles of 0 degrees, 15 degrees, 30 degrees, 45 degrees,60 degrees, and −15 degrees.

Another example of a color scale is the CIELCH color space, where, for agiven illumination condition, L* is a value for lightness, C* is a valuefor chroma, and h° denotes a hue as an angular measurement. In anembodiment, a structurally-colored article having structural color canbe considered as having a “single” color when the color measured for thearticle is less than 10 degrees different or less than 5 degreesdifferent at the h° angular coordinate of the CIELCH color space, atthree or more measured observation or illumination angles selected frommeasured at observation or illumination angles of 0 degrees, 15 degrees,30 degrees, 45 degrees, 60 degrees, and −15 degrees. In certainembodiments, colors which, when measured and assigned values in theCIELCH system that vary by at least 45 degrees in the h° measurements,are considered to be different colors. The structurally-colored articlecan have a change of 10 to about 60 degrees, 10 to about 50 degrees, or10 to about 40 degrees, 10 to about 30 degrees, or 10 to about 20degrees, in the h° measurements of the CIELCH system at three or moremeasured observation or illumination angles. The structurally-coloredarticle can have a change of about 1 to 10 degrees, about 1 to 7.5degrees, or 1 to about 2 degrees, in the h° measurements of the CIELCHsystem at three or more measured observation or illumination angles.

Another system for characterizing color includes the “PANTONE” MatchingSystem (Pantone LLC, Carlstadt, New Jersey, USA), which provides avisual color standard system to provide an accurate method forselecting, specifying, broadcasting, and matching colors through anymedium. In an example, a structurally-colored article having astructural color can be considered as having a “single” color when thecolor measured for the article is within a certain number of adjacentstandards, e.g., within 20 adjacent PANTONE standards, at three or moremeasured observation or illumination angles selected from 0 degrees, 15degrees, 30 degrees, 45 degrees, 60 degrees, and -15 degrees.

Now having described color, additional details regarding the opticalelement are provided. As described herein, the SC filament includes theoptical element or fragments thereof. For simplicity, reference to thestructure of the optical element also includes the fragments of theoptical element unless specifically stated otherwise. The opticalelement can include at least one optical layer. The optical element thatcan be or include a single or multilayer reflector or a multilayerfilter. The optical element can function to modify the light thatimpinges thereupon so that structural color is imparted to the article.The optical element can include at least one optical layer andoptionally one or more additional layers (e.g., a protective layer, thetextured layer, a polymer layer, and the like).

The method of making the structurally colored article or thepolymer-based item can include disposing (e.g., affixing, attaching,bonding, fastening, joining, appending, connecting, binding, andoperably disposed, etc.) the optical element onto the structurallycolored article (e.g., pellet, extruded pellet, sheet, film, and thelike) or a polymer-based item (e.g., pellet, sheet, film, article orcomponent of an article that included the optical element, and thelike). The article has a surface upon which the optical element can bedisposed. The surface of the article can be made of a material such as athermoplastic material, as described herein. The optical element has afirst side (including the outer surface) and a second side opposing thefirst side (including the opposing outer surface).

The optical element or layers or portions thereof (e.g., optical layer)can be formed using known techniques such as physical vapor deposition,electron beam deposition, atomic layer deposition, molecular beamepitaxy, cathodic arc deposition, pulsed laser deposition, sputteringdeposition (e.g., radio frequency, direct current, reactive,non-reactive), chemical vapor deposition, plasma-enhanced chemical vapordeposition, low pressure chemical vapor deposition and wet chemistrytechniques such as layer-by-layer deposition, sol-gel deposition,Langmuir blodgett, and the like.

The optical layer(s) of the optical element can comprise a single layerreflector or a multilayer reflector. The multilayer reflector can beconfigured to have a certain reflectivity at a given wavelength of light(or range of wavelengths) depending, at least in part, on the materialselection, thickness and number of the layers of the multilayerreflector. In other words, one can carefully select the materials,thicknesses, and numbers of the layers of a multilayer reflector andoptionally its interaction with one or more other layers, so that it canreflect a certain wavelength of light (or range of wavelengths), toproduce a desired structural color (e.g., color, iridescence, metallic).The optical layer can include at least two adjacent layers, where theadjacent layers have different refractive indices. The difference in theindex of refraction of adjacent layers of the optical layer can be about0.0001 to 50 percent, about 0.1 to 40 percent, about 0.1 to 30 percent,about 0.1 to 20 percent, about 0.1 to 10 percent (and other ranges therebetween (e.g., the ranges can be in increments of 0.0001 to 5 percent)).The index of refraction depends at least in part upon the material ofthe optical layer and can range from 1.3 to 2.6.

The optical element can include 2 to 20 layers, 2 to 15 layers, 2 to 10layers, 2 to 6 layers, or 2 to 4 layers. Each layer of the opticalelement can have a thickness that is about one-fourth of the wavelengthof light to be reflected to produce the desired structural color. Eachlayer of the optical element can have a thickness of about 10 to 500nanometers or about 90 to 200 nanometers. The optical layer can have atleast two layers, where adjacent layers have different thicknesses andoptionally the same or different refractive indices. The optical elementcan have a thickness of about 100 to 1,500 nanometers, about 100 to1,200 nanometers, about 100 to about 700 nanometers, or of about 200 toabout 500 nanometers.

Each of the layers of the optical element can have a thickness of atleast 10 nanometers, optionally at least 30 nanometers, at least 40nanometers, at least 50 nanometers, optionally at least 60 nanometers,at least 100 nanometers, at least 150 nanometers, optionally a thicknessof from about 10 nanometers to about 250 nanometers or more, about 10nanometers to about 200 nanometers, about 10 nanometers to about 150nanometers, about 10 nanometers to about 100 nanometers, or of fromabout 30 nanometers to about 80 nanometers, or from about 40 nanometersto about 60 nanometers. For example, the each layer can be about 30 to150 nanometers thick. The density of the Ti layer or TiO_(x) layer canbe about 3 to 6 grams per centimeter cubed, about 3 to 5 grams percentimeter cubed, about 4 to 5 grams per centimeter cubed, or 4.5 gramsper centimeter cubed.

The optical element can comprise a single layer filter or a multilayerfilter. The multilayer filter destructively interferes with light thatimpinges upon the structure or article, where the destructiveinterference of the light and optionally interaction with one or moreother layers or structures (e.g., a multilayer reflector, a texturedstructure) impart the structural color. In this regard, the layers ofthe multilayer filter can be designed (e.g., material selection,thickness, number of layer, and the like) so that a single wavelength oflight, or a particular range of wavelengths of light, make up thestructural color. For example, the range of wavelengths of light can belimited to a range within plus or minus 30 percent or a singlewavelength, or within plus or minus 20 percent of a single wavelength,or within plus or minus 10 percent of a single wavelength, or withinplus or minus 5 percent or a single wavelength. The range of wavelengthscan be broader to produce a more iridescent structural color or can bemetallic in nature.

The optical layer(s) can include a single layer or multiple layers whereeach layer independently comprises a material selected from: thetransition metals, the metalloids, the lanthanides, and the actinides,as well as nitrides, oxynitrides, sulfides, sulfates, selenides, andtellurides of these. The material can be selected to provide an index ofrefraction that when optionally combined with the other layers of theoptical element achieves the desired result. One or more layers of theoptical layer can be made of liquid crystals. Each layer of the opticallayer can be made of liquid crystals. One or more layers of the opticallayer can be made of a material such as: silicon dioxide, titaniumdioxide, zinc sulfide, magnesium fluoride, tantalum pentoxide, aluminumoxide, or a combination thereof. Each layer of the optical layer can bemade of a material such as: silicon dioxide, titanium dioxide, zincsulfide, magnesium fluoride, tantalum pentoxide, aluminum oxide, or acombination thereof.

The optical element can be uncolored (e.g., no pigments or dyes added tothe structure or its layers), colored (e.g., pigments and/or dyes areadded to the structure or its layers (e.g., dark or black color)),reflective, and/or transparent (e.g., percent transmittance of 75percent or more). The surface of the article upon which the opticalelement is disposed can be uncolored (e.g., no pigments or dyes added tothe material), colored (e.g., pigments and/or dyes are added to thematerial (e.g., dark or black color)), reflective, and/or transparent(e.g., percent transmittance of 75 percent or more).

The optical layer(s) can be formed in a layer-by-layer manner, whereeach layer has a different index of refraction. Each layer of theoptical layer can be formed using known techniques such as physicalvapor deposition including: chemical vapor deposition, pulsed laserdeposition, evaporative deposition, sputtering deposition (e.g., radiofrequency, direct current, reactive, non-reactive), plasma enhancedchemical vapor deposition, electron beam deposition, atomic layerdeposition, molecular beam epitaxy, cathodic arc deposition, lowpressure chemical vapor deposition and wet chemistry techniques such aslayer by layer deposition, sol-gel deposition, Langmuir blodgett and thelike.

As mentioned above, the optical element can include one or more layersin addition to the optical layer(s). The optical element has a firstside (e.g., the side having a surface) and a second side (e.g., the sidehaving a surface). The one or more other layers of the optical elementcan be on the first side and/or the second side of the optical element.For example, the optical element can include a protective layer and/or apolymeric layer such as a thermoplastic polymeric layer, where theprotective layer and/or the polymeric layer can be on one or both of thefirst side and the second side of the optical element. One or more ofthe optional other layers can include a textured surface. Alternativelyor in addition, one or more optical layers of the optical element caninclude a textured surface.

A portion of the plurality of optical elements or the fragments of theoptical elements are not structurally deteriorated during processingsuch that the optical elements or the fragments thereof have the opticaleffect, while other portions are structurally deteriorated duringprocessing and do not have the optical effect.

The optical element and the fragments of the optical element are layeredstructures having two or more layers stacked in the z dimension,perpendicular to the plane of the layered stack. In addition, theoptical element and the fragments of the optical element have a width inthe x dimension, a length in the y dimension and a thickness in the zdimension. The thickness of the fragments of the optical elements issuch that it imparts an optical effect, where the optical effect of thefragments of the optical elements can be the same or different than theoptical effect of the optical element before processing. The thicknessof the optical elements or fragments of the optical elements in thedispersed in the structurally colored article or the SC filament can beless than 30 percent less, less than 20 percent less, can be less than10 percent less, can be less than 5 percent less, than the thickness ofthe optical element on the polymer-based item (or the pre-process and/orextruded optical element). The width and length of the fragments of theoptical elements dispersed in the polymer-based item can be unchanged orbe about 5 percent, about 10 percent, about 15 percent, about 25percent, about 35 percent, about 50 percent, or smaller than the widthand length of the optical element of the polymer-based item beforeprocessing.

The plurality of optical elements or fragments thereof dispersed in thestructurally colored article or the SC filament can have, independentlyof each other, an average width and an average length of about 400nanometers or more, about 500 nanometer or more, or about 800 nanometersor more. The plurality of optical elements or fragments thereofdispersed in the structurally colored article or the SC filament canhave an average width and an average length of about 400 nanometers ormore, about 500 nanometer or more, or about 800 nanometers or more. Theplurality of optical elements or fragments thereof dispersed in thestructurally colored article or the SC filament can have an averagethickness of about 200 nanometers or more, about 250 nanometers or more,about 300 nanometers or more, about 350 nanometers for more, about 400nanometers or more about 500 nanometers or more, about 600 nanometers ormore, about 800 nanometers, or about 1,000 to 10,000 nanometers or more.

A protective layer can be disposed on the first and/or second side ofthe optical layer to protect the optical layer. The protective layer ismore durable or more abrasion resistant than the optical layer. Theprotective layer is optically transparent to visible light. Theprotective layer can be on the first side of the optical element toprotect the optical layer. All or a portion of the protective layer caninclude a dye or pigment in order to alter an appearance of thestructural color. The protective layer can include silicon dioxide,glass, combinations of metal oxides, or mixtures of polymers. Theprotective layer can have a thickness of about 3 nanometers to 1millimeter. The polymer layer may be removed during the processing orextruding process of the optical layers.

The protective layer can be formed using physical vapor deposition,chemical vapor deposition, pulsed laser deposition, evaporativedeposition, sputtering deposition (e.g., radio frequency, directcurrent, reactive, non-reactive), plasma enhanced chemical vapordeposition, electron beam deposition, cathodic arc deposition, lowpressure chemical vapor deposition and wet chemistry techniques such aslayer by layer deposition, sol-gel deposition, Langmuir blodgett, andthe like. Alternatively or in addition, the protective layer can beapplied by spray coating, dip coating, brushing, spin coating, doctorblade coating, and the like.

A polymeric layer can be disposed on the first and/or the second side ofthe optical element. The polymeric layer can be used to dispose theoptical element onto an article, such as, for example, when the articledoes not include a thermoplastic material to adhere the optical element.The polymeric layer can comprise a polymeric adhesive material, such asa hot melt adhesive. The polymeric layer can be a thermoplastic materialand can include one or more layers. The thermoplastic material can beany one of the thermoplastic material described herein. The polymericlayer can be applied using various methodologies, such as spin coating,dip coating, doctor blade coating, and so on. The polymeric layer canhave a thickness of about 3 nanometer to 1 millimeter.

Having described the optical element, additional details will now bedescribed for the optional textured surface. As described herein, theoptical element can include at least one optical layer and optionally atextured surface. The textured surface can be a surface of a texturedstructure or a textured layer. The textured surface or textured layermay be provided as part of the optical element. For example, the opticalelement may comprise a textured layer or a textured structure thatcomprises the textured surface. The textured surface may be formed onthe first or second side of the optical element. For example, a side ofthe optical element can be formed or modified to provide a texturedsurface, or a textured layer or textured structure can be disposed on(e.g., affixed to) the first or second side of the optical element. Thetextured surface may be provided as part of the article to which theoptical element is disposed, in which case the optical element has thetopography or similar topography as the textured surface. For example,the optical element may be disposed onto the surface of the articlewhere the surface of the article is a textured surface, or the surfaceof the article includes a textured structure or a textured layer.

The textured surface (or a textured structure or textured layerincluding the textured surface) may be provided as a feature on or partof another medium, such as a transfer medium, and imparted to a side orlayer of the optical element or to the surface of the article. Forexample, a mirror image or relief form of the textured surface may beprovided on the side of a transfer medium, and the transfer mediumcontacts a side of the optical element or the surface of the article ina way that imparts the textured surface to the optical element orarticle. While the various embodiments herein may be described withrespect to a textured surface of the optical element, it will beunderstood that the features of the textured surface, or a texturedstructure or textured layer, may be imparted in any of these ways.

The textured surface can contribute to the structural color resultingfrom the optical element. As described herein, structural coloration isimparted, at least in part, due to optical effects resulting fromphysical phenomena such as scattering, diffraction, reflection,interference or unequal refraction of light rays from an opticalelement. The textured surface (or its mirror image or relief) caninclude a plurality of profile features and flat or planar areas. Theplurality of profile features included in the textured surface,including their size, shape, orientation, spatial arrangement, etc., canaffect the light scattering, diffraction, reflection, interferenceand/or refraction resulting from the optical element. The flat or planarareas included in the textured surface, including their size, shape,orientation, spatial arrangement, etc., can affect the light scattering,diffraction, reflection, interference and/or refraction resulting fromthe optical element. The desired structural color can be designed, atleast in part, by adjusting one or more of properties of the profilefeatures and/or flat or planar areas of the textured surface.

The profile features can extend from a side of the flat areas, so as toprovide the appearance of projections and/or depressions therein. In anaspect, the flat areas can be flat planar areas. A profile feature mayinclude various combinations of projections and depressions. Forexample, a profile feature may include a projection with one or moredepressions therein, a depression with one or more projections therein,a projection with one or more further projections thereon, a depressionwith one or more further depressions therein, and the like. The flatareas do not have to be completely flat and can include texture,roughness, and the like. The texture of the flat areas may notcontribute much, if any, to the imparted structural color. The textureof the flat areas typically contributes to the imparted structuralcolor. For clarity, the profile features and flat areas are described inreference to the profile features extending above the flat areas, butthe inverse (e.g., dimensions, shapes, and the like) can apply when theprofile features are depressions in the textured surface.

The textured surface can comprise a thermoplastic material. The profilefeatures and the flat areas can be formed using a thermoplasticmaterial.

The textured surface generally has a length dimension extending along anx-axis, and a width dimension extending along a z-axis, and a thicknessdimension extending along a y-axis. The textured surface has a generallyplanar portion extending in a first plane that extends along the x-axisand the z-axis. A profile feature can extend outward from the firstplane, so as to extend above or below the plane x. A profile feature mayextend generally orthogonal to the first plane, or at an angle greaterto or less than 90 degrees to the first plane.

The dimensional measurements in reference to the profile features (e.g.,length, width, height, diameter, and the like) described herein refer toan average dimensional measurement of profile features in 1 squarecentimeter in the inorganic optical element.

The dimension (e.g., length, width, height, diameter, depending upon theshape of the profile feature) of each profile feature can be within thenanometer to micrometer range. A textured surface can have a profilefeature and/or flat area with a dimension of about 10 nanometers toabout 500 micrometers. The profile feature can have dimensions in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. All of the dimensions of the profile feature (e.g., length,width, height, diameter, depending on the geometry) can be in thenanometer range, e.g., from about 10 nanometers to about 1000nanometers. The textured surface can have a plurality of profilefeatures having dimensions that are 1 micrometer or less. In thiscontext, the phrase “plurality of the profile features” is meant to meanthat about 50 percent or more, about 60 percent or more, about 70percent or more, about 80 percent or more, about 90 percent or more, orabout 99 percent or more of the profile features have a dimension inthis range. The profile features can have a ratio of width:height and/orlength:height dimensions of about 1:2 and 1:100, or 1:5 and 1:50, or 1:5and 1:10.

The textured surface can have a profile feature and/or flat area with adimension within the micrometer range of dimensions. A textured surfacecan have a profile feature and/or flat area with a dimension of about 1micrometer to about 500 micrometers. All of the dimensions of theprofile feature (e.g., length, width, height, diameter, depending on thegeometry) can be in the micrometer range, e.g., from about 1 micrometerto about 500 micrometers. The textured surface can have a plurality ofprofile features having dimensions that are from about 1 micrometer toabout 500 micrometer. In this context, the phrase “plurality of theprofile features” is meant to mean that about 50 percent or more, about60 percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have a dimension in this range. The height of the profilefeatures (or depth if depressions) can be about 0.1 and 50 micrometers,about 1 to 5 micrometers, or 2 to 3 micrometers. The profile featurescan have a ratio of width:height and/or length:height dimensions ofabout 1:2 and 1:100, or 1:5 and 1:50, or 1:5 and 1:10.

A textured surface can have a plurality of profile features having amixture of size dimensions within the nanometer to micrometer range(e.g., a portion of the profile features are on the nanometer scale anda portion of the profile features are on the micrometer scale). Atextured surface can have a plurality of profile features having amixture of dimensional ratios. The textured surface can have a profilefeature having one or more nanometer-scale projections or depressions ona micrometer-scale projection or depression.

The profile feature can have height and width dimensions that are withina factor of three of each other (0.33w≤h≤3w where w is the width and his the height of the profile feature) and/or height and lengthdimensions that are within a factor of three of each other (0.33I≤h≤3Iwhere I is the length and h is the height of the profile feature). Theprofile feature can have a ratio of length:width that is from about 1:3to about 3:1, or about 1:2 to about 2:1, or about 1:1.5 to about 1.5:1,or about 1:1.2 to about 1.2:1, or about 1:1. The width and length of theprofile features can be substantially the same or different.

In another aspect, the textured surface can have a profile featureand/or flat area with at least one dimension in the mid-micrometer rangeand higher (e.g., greater than 500 micrometers). The profile feature canhave at least one dimension (e.g., the largest dimension such as length,width, height, diameter, and the like depending upon the geometry orshape of the profile feature) of greater than 500 micrometers, greaterthan 600 micrometers, greater than 700 micrometers, greater than 800micrometers, greater than 900 micrometers, greater than 1000micrometers, greater than 2 millimeters, greater than 10 millimeters, ormore. For example, the largest dimension of the profile feature canrange from about 600 micrometers to about 2000 micrometers, or about 650micrometers to about 1500 micrometers, or about 700 micrometers to about1000 micrometers. At least one or more of the dimensions of the profilefeature (e.g., length, width, height, diameter, depending on thegeometry) can be in the micrometer range, while one or more of the otherdimensions can be in the nanometer to micrometer range (e.g., less than500 micrometers, less than 100 micrometers, less than 10 micrometers, orless than 1 micrometer). The textured surface can have a plurality ofprofile features having at least one dimension that is in themid-micrometer or more range (e.g., 500 micrometers or more). In thiscontext, the phrase “plurality of the profile features” is meant to meanthat about 50 percent or more, about 60 percent or more, about 70percent or more, about 80 percent or more, about 90 percent or more, orabout 99 percent or more of the profile features have at least onedimension that is greater than 500 micrometers. In particular, at leastone of the length and width of the profile feature is greater than 500micrometers or both the length and the width of the profile feature isgreater than 500 micrometers. In another example, the diameter of theprofile feature is greater than 500 micrometers. In another example,when the profile feature is an irregular shape, the longest dimension isgreater than 500 micrometers.

In aspects, the height of the profile features can be greater than 50micrometers. In this context, the phrase “plurality of the profilefeatures” is meant to mean that about 50 percent or more, about 60percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have at height that is greater than 50 micrometers. The heightof the profile feature can be 50 micrometers, about 60 micrometers,about 70 micrometers, about 80 micrometers, about 90 micrometers, orabout 100 micrometers to about 60 micrometers, about 70 micrometers,about 80 micrometers, about 90 micrometers, about 100 micrometers, about150 micrometers, about 250 micrometers, about 500 micrometers or more.For example, the ranges can include 50 micrometers to 500 micrometers,about 60 micrometers to 250 micrometers, about 60 micrometers to about150 micrometers, and the like. One or more of the other dimensions(e.g., length, width, diameter, or the like) can be in the nanometer tomicrometer range (e.g., less than 500 micrometers, less than 100micrometers, less than 10 micrometers, or less than 1 micrometer). Inparticular, at least one of the length and width of the profile featureis less than 500 micrometers or both the length and the width of theprofile feature is less than 500 micrometers, while the height isgreater than 50 micrometers. One or more of the other dimensions (e.g.,length, width, diameter, or the like) can be in the micrometer tomillimeter range (e.g., greater than 500 micrometers to 10 millimeters).

The dimension (e.g., length, width, height, diameter, depending upon theshape of the profile feature) of each profile feature can be within thenanometer to micrometer range. The textured surface can have a profilefeature and/or flat area with a dimension of about 10 nanometers toabout 500 micrometers or higher (e.g., about 1 millimeter, about 2millimeters, about 5 millimeters, or about 10 millimeters). At least oneof the dimensions of the profile feature (e.g., length, width, height,diameter, depending on the geometry) can be in the nanometer range(e.g., from about 10 nanometers to about 1000 nanometers), while atleast one other dimension (e.g., length, width, height, diameter,depending on the geometry) can be in the micrometer range (e.g., 5micrometers to 500 micrometers or more (e.g., about 1 to 10millimeters)). The textured surface can have a plurality of profilefeatures having at least one dimension in the nanometer range (e.g.,about 10 to 1000 nanometers) and the other in the micrometer range(e.g., 5 micrometers to 500 micrometers or more). In this context, thephrase “plurality of the profile features” is meant to mean that about50 percent or more, about 60 percent or more, about 70 percent or more,about 80 percent or more, about 90 percent or more, or about 99 percentor more of the profile features have at least one dimension in thenanometer range and at least one dimension in the micrometer range. Inparticular, at least one of the length and width of the profile featureis in the nanometer range, while the other of the length and the widthof the profile feature is in the micrometer range.

In aspects, the height of the profile features can be greater than 250nanometers. In this context, the phrase “plurality of the profilefeatures” is meant to mean that about 50 percent or more, about 60percent or more, about 70 percent or more, about 80 percent or more,about 90 percent or more, or about 99 percent or more of the profilefeatures have at height that is greater than 250 nanometers. The heightof the profile feature can be 250 nanometers, about 300 nanometers,about 400 nanometers, or about 500 nanometers, to about 300 nanometers,about 400 nanometers, about 500 nanometers, or about 1000 nanometers ormore. For example, the range can be 250 nanometers to about 1000nanometers, about 300 nanometers to 500 nanometers, about 400 nanometersto about 1000 nanometers, and the like. One or more of the otherdimensions (e.g., length, width, diameter, or the like) can be in themicrometer to millimeter range (e.g., greater than 500 micrometers to 10millimeters). In particular, at least one of the length and width of theprofile feature is in the nanometer range (e.g., about 10 to 1000nanometers) and the other in the micrometer range (e.g., 5 micrometersto 500 micrometers or more), while the height is greater than 250nanometers.

The profile features can have a certain spatial arrangement. The spatialarrangement of the profile features may be uniform, such as spacedevenly apart or forming a pattern. The spatial arrangement can berandom. Adjacent profile features can be about 10 to 500 nanometersapart, about 100 to 1000 nanometers apart, about 1 to 100 micrometersapart or about 5 to 100 micrometers apart. Adjacent profile features canoverlap one another or be adjacent one another so little or no flatregions are positioned there between. The desired spacing can depend, atleast in part, on the size and/or shape of the profile structures andthe desired structural color effect.

The profile features can have a certain cross-sectional shape (withrespect to a plane parallel the first plane). The textured surface canhave a plurality of profile features having the same or similarcross-sectional shape. The textured surface has a plurality of profilefeatures having a mixture of different cross-sectional shapes. Thecross-sectional shapes of the profile features can include polygonal(e.g., square or triangle or rectangle cross section), circular,semi-circular, tubular, oval, random, high and low aspect ratios,overlapping profile features, and the like.

The profile feature (e.g., about 10 nanometers to 500 micrometers) caninclude an upper, flat surface. The profile feature (e.g., about 10nanometers to 500 micrometers) can include an upper, concavely curvedsurface. The concave curved surface may extend symmetrically either sideof an uppermost point. The concave curved surface may extendsymmetrically across only 50 percent of the uppermost point. The profilefeature (e.g., about 10 nanometers to 500 micrometers) can include anupper, convexly curved surface. The curved surface may extendsymmetrically either side of an uppermost point. The curved surface mayextend symmetrically across only 50 percent of the uppermost point.

The profile feature can include protrusions from the textured surface.The profile feature can include indents (hollow areas) formed in thetextured surface. The profile feature can have a smooth, curved shape(e.g., a polygonal cross-section with curved corners).

The profile features (whether protrusions or depressions) can beapproximately conical or frusto-conical (i.e. the projections or indentsmay have horizontally or diagonally flattened tops) or have anapproximately part-spherical surface (e.g., a convex or concave surfacerespectively having a substantially even radius of curvature).

The profile features may have one or more sides or edges that extend ina direction that forms an angle to the first plane of the texturedsurface. The angle between the first plane and a side or edge of theprofile feature is about 45 degrees or less, about 30 degrees or less,about 25 degrees or less, or about 20 degrees or less. The one or moresides or edges may extend in a linear or planar orientation or may becurved so that the angle changes as a function of distance from thefirst plane. The profile features may have one or more sides thatinclude step(s) and/or flat side(s). The profile feature can have one ormore sides (or portions thereof) that can be orthogonal or perpendicularto the first plane of the textured surface, or extend at an angle ofabout 10 degrees to 89 degrees to the first plane (90 degrees beingperpendicular or orthogonal to the first plane)). The profile featurecan have a side with a stepped configuration, where portions of the sidecan be parallel to the first plane of the textured surface or have anangle of about 1 degree to 179 degrees (0 degrees being parallel to thefirst plane)).

The textured surface can have profile features with varying shapes(e.g., the profile features can vary in shape, height, width and lengthamong the profile features) or profile features with substantiallyuniform shapes and/or dimensions. The structural color produced by thetextured surface can be determined, at least in part, by the shape,dimensions, spacing, and the like, of the profile features.

The profile features can be shaped so as to result in a portion of thesurface (e.g., about 25 to 50 percent or more) being about normal to theincoming light when the light is incident at the normal to the firstplane of the textured surface. The profile features can be shaped so asto result in a portion of the surface (e.g., about 25 to 50 percent ormore) being about normal to the incoming light when the light isincident at an angle of up to 45 degrees to the first plane of thetextured surface.

The spatial orientation of the profile features on the textured surfacecan be used to produce the structural color, or to effect the degree towhich the structural color shifts at different viewing angles. Thespatial orientation of the profile features on the textured surface canbe random, a semi-random pattern, or in a set pattern. A set pattern ofprofile features is a known set up or configuration of profile featuresin a certain area (e.g., about 50 nanometers squared to about 10millimeters squared depending upon the dimensions of the profilefeatures (e.g., any increment between about 50 nanometers and about 10millimeters is included)). A semi-random pattern of profile features isa known set up of profile features in a certain area (e.g., about 50nanometers squared to 10 millimeters squared) with some deviation (e.g.,1 to 15% deviation from the set pattern), while random profile featuresare present in the area but the pattern of profile features isdiscernable. A random spatial orientation of the profile features in anarea produces no discernable pattern in a certain area, (e.g., about 50nanometers squared to 10 millimeters squared).

The spatial orientation of the profile features can be periodic (e.g.,full or partial) or non-periodic. A periodic spatial orientation of theprofile features is a recurring pattern at intervals. The periodicity ofthe periodic spatial orientation of the profile features can depend uponthe dimensions of the profile features but generally are periodic fromabout 50 nanometers to 100 micrometers. For example, when the dimensionsof the profile features are submicron, the periodicity of the periodicspatial orientation of the profile features can be in the 50 to 500nanometer range or 100 to 1000 nanometer range. In another example, whenthe dimensions of the profile features are at the micron level, theperiodicity of the periodic spatial orientation of the profile featurescan be in the 10 to 500 micrometer range or 10 to 1000 micrometer range.Full periodic pattern of profile features indicates that the entirepattern exhibits periodicity, whereas partial periodicity indicates thatless than all of the pattern exhibits periodicity (e.g., about 70-99percent of the periodicity is retained). A non-periodic spatialorientation of profile features is not periodic and does not showperiodicity based on the dimensions of the profile features, inparticular, no periodicity in the 50 to 500 nanometer range or 100 to1000 nanometer range where the dimensions are of the profile featuresare submicron or no periodicity in the 10 to 500 micrometer range or 10to 1000 micrometer range where the dimensions are of the profilefeatures are in the micron range.

In an aspect, the spatial orientation of the profile features on thetextured surface can be set to reduce distortion effects, e.g., causedby the interference of one profile feature with another in regard to thestructural color of the article. Since the shape, dimension, relativeorientation of the profile features can vary considerably across thetextured surface, the desired spacing and/or relative positioning for aparticular area (e.g., in the micrometer range or about 1 to 10 squaremicrometers) having profile features can be appropriately determined. Asdiscussed herein, the shape, dimension, relative orientation of theprofile features affect the contours of the reflective layer(s) and/orconstituent layer(s), so the dimensions (e.g., thickness), index ofrefraction, number of layers in the inorganic optical element (e.g.,reflective layer(s) and constituent layer(s)) are considered whendesigning the textured side of the texture layer.

The profile features are located in nearly random positions relative toone another across a specific area of the textured surface (e.g., in themicrometer range or about 1 to 10 square micrometers to centimeter rangeor about 0.5 to 5 square centimeters, and all range increments therein),where the randomness does not defeat the purpose of producing thestructural color. In other words, the randomness is consistent with thespacing, shape, dimension, and relative orientation of the profilefeatures, the dimensions (e.g., thickness), index of refraction, andnumber of layers (e.g., the reflective layer(s), the constituentlayer(s), and the like, with the goal to achieve the structural color.

The profile features are positioned in a set manner relative to oneanother across a specific area of the textured surface to achieve thepurpose of producing the structural color. The relative positions of theprofile features do not necessarily follow a pattern, but can follow apattern consistent with the desired structural color. As mentioned aboveand herein, various parameters related to the profile features, flatareas, and reflective layer(s) and/or the constituent layer can be usedto position the profile features in a set manner relative to oneanother.

The textured surface can include micro and/or nanoscale profile featuresthat can form gratings (e.g., a diffractive grating), photonic crystalstructure, a selective mirror structure, crystal fiber structures,deformed matrix structures, spiraled coiled structures, surface gratingstructures, and combinations thereof. The textured surface can includemicro and/or nanoscale profile features that form a grating having aperiodic or non-periodic design structure to impart the structuralcolor. The micro and/or nanoscale profile features can have apeak-valley pattern of profile features and/or flat areas to produce thedesired structural color. The grading can be an Echelette grating.

The profile features and the flat areas of the textured surface in theinorganic optical element can appear as topographical undulations ineach layer (e.g., reflective layer(s) and/or the constituent layer(s)).For example, referring to FIG. 2A, an inorganic optical element 200includes a textured structure 220 having a plurality of profile features222 and flat areas 224. As described herein, one or more of the profilefeatures 222 can be projections from a surface of the textured structure220, and/or one or more of the profile features can be depressions in asurface of the textured structure 220 (not shown). One or moreconstituent layers 240 are disposed on the textured structure 220 andthen a reflective layer 230 and one or more constituent layers 245 aredisposed on the preceding layers. In some embodiments, the resultingtopography of the textured structure 220 and the one or more constituentlayers 240 and 245 and the reflective layer 230 are not identical, butrather, the one or more constituent layers 240 and 245 and thereflective layer 230 can have elevated or depressed regions 242 whichare either elevated or depressed relative to the height of the planarregions 244 and which roughly correspond to the location of the profilefeatures 222 of the textured structure 220. The one or more constituentlayers 240 and 245 and the reflective layer 230 have planar regions 244that roughly correspond to the location of the flat areas 224 of thetextured structure 220. Due to the presence of the elevated or depressedregions 242 and the planar regions 244, the resultant overall topographyof the one or more constituent layers 240 and 245 and the reflectivelayer 230 can be that of an undulating or wave-like structure. Thedimension, shape, and spacing of the profile features along with thenumber of layers of the constituent layer, the reflective layer, thethickness of each of the layers, refractive index of each layer, and thetype of material, can be used to produce an inorganic optical elementwhich results in a particular structural color.

While the textured surface can produce the structural color in someembodiments, or can affect the degree to which the structural colorshifts at different viewing angles, in other embodiments, a “texturedsurface” or surface with texture may not produce the structural color,or may not affect the degree to which the structural color shifts atdifferent viewing angles. The structural color can be produced by thedesign of the inorganic optical element with or without the texturedsurface. As a result, the inorganic optical element can include thetextured surface having profile elements of dimensions in the nanometerto millimeter range, but the structural color or the shifting of thestructural color is not attributable to the presence or absence of thetextured surface. In other words, the inorganic optical element impartsthe same structural color where or not the textured surface is presentThe design of the textured surface can be configured to not affect thestructural color imparted by the inorganic optical element, or notaffect the shifting of the structural color imparted by the inorganicoptical element. The shape of the profile features, dimensions of theshapes, the spatial orientation of the profile features relative to oneanother, and the like can be selected so that the textured surface doesnot affect the structural color attributable to the inorganic opticalelement.

The structural color imparted by a first inorganic optical element and asecond inorganic optical element, where the only difference between thefirst and second inorganic optical element is that the first inorganicoptical element includes the textured surface, can be compared. A colormeasurement can be performed for each of the first and second inorganicoptical element at the same relative angle, where a comparison of thecolor measurements can determine what, if any, change is correlated tothe presence of the textured surface. For example, at a firstobservation angle the structural color is a first structural color forthe first inorganic optical element and at first observation angle thestructural color is a second structural color for the second inorganicoptical element. The first color measurement can be obtained and hascoordinates L₁* and a₁* and b₁*, while a second color measurement can beobtained and has coordinates L₂* and a₂* and b₂* can be obtained,according to the CIE 1976 color space under a given illuminationcondition.

When ΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 2.2 or is less than or equalto about 3, the first structural color associated with the first colormeasurement and the second structural color associated with the secondcolor measurement are the same or not perceptibly different to anaverage observer (e.g., the textured surface does not cause or changethe structural color by more than 20 percent, 10 percent, or 5 percent).When ΔE*_(ab) between the first color measurement and the second colormeasurement is greater than 3 or optionally greater than about 4 or 5,the first structural color associated with the first color measurementand the second structural color associated with the second colormeasurement are different or perceptibly different to an averageobserver (e.g., the textured surface does cause or change the structuralcolor by more than 20 percent, 10 percent, or 5 percent).

In another approach, when the percent difference between one or more ofvalues L₁* and L₂* a₁* and a₂*, and b₁* and b₂* is less than 20 percent,the first structural color associated with the first color measurementand the second structural color associated with the second colormeasurement are the same or not perceptibly different to an averageobserver (e.g., the textured surface does not cause or change thestructural color by less than 20 percent, 10 percent, or 5 percent).When the percent difference between one or more of values L₁* and L₂*a₁* and a₂*, and b₁* and b₂* is greater than 20 percent, the firststructural color associated with the first color measurement and thesecond structural color associated with the second color measurement aredifferent or perceptibly different to an average observer (e.g., thetextured surface does cause or change the structural color by more than20 percent, 10 percent, or 5 percent).

In another case, the structural color imparted by a first inorganicoptical element and a second inorganic optical element, where the onlydifferent between the first and second inorganic optical element is thatthe first inorganic optical element includes the textured surface, canbe compared at different angles of incident light upon the inorganicoptical element or different observation angles. A color measurement canbe performed for each of the first and second inorganic optical elementat different angles (e.g., angle of about −15 and 180 degrees or about−15 degrees and +60 degrees and which are at least 15 degrees apart fromeach other), where a comparison of the color measurements can determinewhat, if any, change is correlated to the presence of the texturedsurface a different angles. For example, at a first observation anglethe structural color is a first structural color for the first inorganicoptical element and at second observation angle the structural color isa second structural color for the second inorganic optical element. Thefirst color measurement can be obtained and has coordinates L₁* and a₁*and b₁*, while a second color measurement can be obtained and hascoordinates L₂* and a₂* and b₂* can be obtained, according to the CIE1976 color space under a given illumination condition.

When ΔE*_(ab) between the first color measurement and the second colormeasurement is less than or equal to about 2.2 or is less than or equalto about 3, the first structural color associated with the first colormeasurement and the second structural color associated with the secondcolor measurement are the same or not perceptibly different to anaverage observer (e.g., the textured surface does not cause or changethe structural color based on different angles of incident light uponthe inorganic optical element or different observation angles). WhenΔE*_(ab) between the first color measurement and the second colormeasurement is greater than 3 or optionally greater than about 4 or 5,the first structural color associated with the first color measurementand the second structural color associated with the second colormeasurement are different or perceptibly different to an averageobserver (e.g., the textured surface does cause or change the structuralcolor at different angles of incident light upon the inorganic opticalelement or different observation angles).

In another approach, when the percent difference between one or more ofvalues L₁* and L₂* a₁* and a₂*, and b₁* and b₂* is less than 20 percent,the first structural color associated with the first color measurementand the second structural color associated with the second colormeasurement are the same or not perceptibly different to an averageobserver (e.g., the textured surface does not cause or change thestructural color by more than 20 percent, 10 percent, or 5 percent atdifferent angles of incident light upon the inorganic optical element ordifferent observation angles). When the percent difference between oneor more of values L₁* and L₂* a₁* and a₂*, and b₁* and b₂* is greaterthan 20 percent, the first structural color associated with the firstcolor measurement and the second structural color associated with thesecond color measurement are different or perceptibly different to anaverage observer (e.g., the textured surface does cause or change thestructural color by more than 20 percent, 10 percent, or 5 percent atdifferent angles of incident light upon the inorganic optical element ordifferent observation angles).

In another embodiment, the structural color can be imparted by theinorganic optical element without the textured surface. The surface ofthe layers of the optical element are substantially flat (orsubstantially three-dimensional flat planar surface) or flat (orthree-dimensional flat planar surface) at the microscale (e.g., about 1to 500 micrometers) and/or nanoscale (e.g., about 50 to 500 nanometers).In regard to substantially flat or substantially planar the surface caninclude some minor topographical features (e.g., nanoscale and/ormicroscale) such as those that might be caused due to unintentionalimperfections, slight undulations that are unintentional, othertopographical features (e.g., extensions above the plane of the layer ordepressions below or into the plane of the layer) caused by theequipment and/or process used and the like that are unintentionallyintroduced. The topographical features do not resemble profile featuresof the textured surface. In addition, the substantially flat (orsubstantially three dimensional flat planar surface) or flat (or threedimensional flat planar surface) may include curvature as the dimensionsof the optical element increase, for example about 500 micrometers ormore, about 10 millimeter or more, about 10 centimeters or more,depending upon the dimensions of the inorganic optical element, as longas the surface is flat or substantially flat and the surface onlyincludes some minor topographical features.

FIG. 2B is a cross-section illustration of a substantially flat (orsubstantially three-dimensional flat planar surface) or flat (or threedimensional flat planar surface) inorganic optical element 300. Theinorganic optical element 300 includes one or more constituent layers340 are disposed on the flat or three-dimensional flat planar surfacestructure 320 and then a reflective layer 330 and one or moreconstituent layers 345 are disposed on the preceding layers. Thematerial that makes up the constituent layers and the reflective layer,number of layers of the constituent layer, the reflective layer, thethickness of each of the layers, refractive index of each layer, and thelike, can produce an inorganic optical element which results in aparticular structural color.

Additional details are provided regarding the polymeric materialsreferenced herein for example, the polymers described in reference tothe filaments, fibers, yarns, polymer-based item, articles ofmanufacture, components of the article, structures, layers, films,sheets, foams, and like the. The polymer can be a thermoplastic polymer.The polymer can be an elastomeric polymer, including an elastomericthermoplastic polymer. The polymer can be selected from: polyurethanes(including elastomeric polyurethanes, thermoplastic polyurethanes(TPUs), and elastomeric TPUs), polyesters, polyethers, polyamides, vinylpolymers (e.g., copolymers of vinyl alcohol, vinyl esters, ethylene,acrylates, methacrylates, styrene, and so on), polyacrylonitriles,polyphenylene ethers, polycarbonates, polyureas, polystyrenes,co-polymers thereof (including polyester-polyurethanes,polyether-polyurethanes, polycarbonate-polyurethanes, polyether blockpolyamides (PEBAs), and styrene block copolymers) , and any combinationthereof, as described herein. The polymer can include one or morepolymers selected from the group consisting of polyesters, polyethers,polyamides, polyurethanes, polyolefins copolymers of each, andcombinations thereof.

The term “polymer” refers to a chemical compound formed of a pluralityof repeating structural units referred to as monomers. Polymers oftenare formed by a polymerization reaction in which the plurality ofstructural units become covalently bonded together. When the monomerunits forming the polymer all have the same chemical structure, thepolymer is a homopolymer. When the polymer includes two or more monomerunits having different chemical structures, the polymer is a copolymer.One example of a type of copolymer is a terpolymer, which includes threedifferent types of monomer units. The co-polymer can include two or moredifferent monomers randomly distributed in the polymer (e.g., a randomco-polymer). Alternatively, one or more blocks containing a plurality ofa first type of monomer can be bonded to one or more blocks containing aplurality of a second type of monomer, forming a block copolymer. Asingle monomer unit can include one or more different chemicalfunctional groups.

Polymers having repeating units which include two or more types ofchemical functional groups can be referred to as having two or moresegments. For example, a polymer having repeating units of the samechemical structure can be referred to as having repeating segments.Segments are commonly described as being relatively harder or softerbased on their chemical structures, and it is common for polymers toinclude relatively harder segments and relatively softer segments bondedto each other in a single monomeric unit or in different monomericunits. When the polymer includes repeating segments, physicalinteractions or chemical bonds can be present within the segments orbetween the segments or both within and between the segments. Examplesof segments often referred to as hard segments include segmentsincluding a urethane linkage, which can be formed from reacting anisocyanate with a polyol to form a polyurethane. Examples of segmentsoften referred to as soft segments include segments including an alkoxyfunctional group, such as segments including ether or ester functionalgroups, and polyester segments. Segments can be referred to based on thename of the functional group present in the segment (e.g., a polyethersegment, a polyester segment), as well as based on the name of thechemical structure which was reacted in order to form the segment (e.g.,a polyol-derived segment, an isocyanate-derived segment). When referringto segments of a particular functional group or of a particular chemicalstructure from which the segment was derived, it is understood that thepolymer can contain up to 10 mole percent of segments of otherfunctional groups or derived from other chemical structures. Forexample, as used herein, a polyether segment is understood to include upto 10 mole percent of non-polyether segments.

As previously described, the polymer can be a thermoplastic polymer. Ingeneral, a thermoplastic polymer softens or melts when heated andreturns to a solid state when cooled. The thermoplastic polymertransitions from a solid state to a softened state when its temperatureis increased to a temperature at or above its softening temperature, anda liquid state when its temperature is increased to a temperature at orabove its melting temperature. When sufficiently cooled, thethermoplastic polymer transitions from the softened or liquid state tothe solid state. As such, the thermoplastic polymer may be softened ormelted, molded, cooled, re-softened or re-melted, re-molded, and cooledagain through multiple cycles. For amorphous thermoplastic polymers, thesolid state is understood to be the “rubbery” state above the glasstransition temperature of the polymer. The thermoplastic polymer canhave a melting temperature from about 90 degrees C. to about 190 degreesC. when determined in accordance with ASTM D3418-97 as described hereinbelow, and includes all subranges therein in increments of 1 degree. Thethermoplastic polymer can have a melting temperature from about 93degrees C. to about 99 degrees C. when determined in accordance withASTM D3418-97 as described herein below. The thermoplastic polymer canhave a melting temperature from about 112 degrees C. to about 118degrees C. when determined in accordance with ASTM D3418-97 as describedherein below.

The glass transition temperature is the temperature at which anamorphous polymer transitions from a relatively brittle “glassy” stateto a relatively more flexible “rubbery” state. The thermoplastic polymercan have a glass transition temperature from about −20 degrees C. toabout 30 degrees C. when determined in accordance with ASTM D3418-97 asdescribed herein below. The thermoplastic polymer can have a glasstransition temperature (from about −13 degree C. to about −7 degrees C.when determined in accordance with ASTM D3418-97 as described hereinbelow. The thermoplastic polymer can have a glass transition temperaturefrom about 17 degrees C. to about 23 degrees C. when determined inaccordance with ASTM D3418-97 as described herein below.

The thermoplastic polymer can have a melt flow index from about 10 toabout 30 cubic centimeters per 10 minutes (cm³/₁0 min) when tested inaccordance with ASTM D1238-13 as described herein below at 160 degreesC. using a weight of 2.16 kilograms (kg). The thermoplastic polymer canhave a melt flow index from about 22 cm³/₁0 min to about 28 cm³/₁0 minwhen tested in accordance with ASTM D1238-13 as described herein belowat 160 degrees C. using a weight of 2.16 kg.

The thermoplastic polymer can have a cold Ross flex test result of about120,000 to about 180,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below. Thethermoplastic polymer can have a cold Ross flex test result of about140,000 to about 160,000 cycles without cracking or whitening whentested on a thermoformed plaque of the thermoplastic polymer inaccordance with the cold Ross flex test as described herein below.

The thermoplastic polymer can have a modulus from about 5 megaPascals(MPa) to about 100 MPa when determined on a thermoformed plaque inaccordance with ASTM D412-98 Standard Test Methods for Vulcanized Rubberand Thermoplastic Rubbers and Thermoplastic Elastomers-Tension withmodifications described herein below. The thermoplastic polymer can havea modulus from about 20 MPa to about 80 MPa when determined on athermoformed plaque in accordance with ASTM D412-98 Standard TestMethods for Vulcanized Rubber and Thermoplastic Rubbers andThermoplastic Elastomers-Tension with modifications described hereinbelow.

Polyurethane

The polymer can be a polyurethane, such as a thermoplastic polyurethane(also referred to as “TPU”). Additionally, polyurethane can be anelastomeric polyurethane, including an elastomeric TPU. The elastomericpolyurethane can include hard and soft segments. The hard segments cancomprise or consist of urethane segments (e.g., isocyanate-derivedsegments). The soft segments can comprise or consist of alkoxy segments(e.g., polyol-derived segments including polyether segments, orpolyester segments, or a combination of polyether segments and polyestersegments). The polyurethane can comprise or consist essentially of anelastomeric polyurethane having repeating hard segments and repeatingsoft segments.

One or more of the polyurethanes can be produced by polymerizing one ormore isocyanates with one or more polyols to produce polymer chainshaving carbamate linkages (−N(CO)O−) as illustrated below in Formula 1,where the isocyanate(s) each preferably include two or more isocyanate(—NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups permolecule (although, mono-functional isocyanates can also be optionallyincluded, e.g., as chain terminating units).

Each R₁ group and R₂ group independently is an aliphatic or aromaticgroup. Optionally, each R₂ can be a relatively hydrophilic group,including a group having one or more hydroxyl groups.

Additionally, the isocyanates can also be chain extended with one ormore chain extenders to bridge two or more isocyanates, increasing thelength of the hard segment. This can produce polyurethane polymer chainsas illustrated below in Formula 2, where R₃ includes the chain extender.As with each R₁ and R₂, each R₃ independently is an aliphatic oraromatic functional group..

Each R₁ group in Formulas 1 and 2 can independently include a linear orbranched group having from 3 to 30 carbon atoms, based on the particularisocyanate(s) used, and can be aliphatic, aromatic, or include acombination of aliphatic portions(s) and aromatic portion(s). The term“aliphatic” refers to a saturated or unsaturated organic molecule orportion of a molecule that does not include a cyclically conjugated ringsystem having delocalized pi electrons. In comparison, the term“aromatic” refers to an organic molecule or portion of a molecule havinga cyclically conjugated ring system with delocalized pi electrons, whichexhibits greater stability than a hypothetical ring system havinglocalized pi electrons.

Each R₁ group can be present in an amount of about 5 percent to about 85percent by weight, from about 5 percent to about 70 percent by weight,or from about 10 percent to about 50 percent by weight, based on thetotal weight of the reactant compounds or monomers which form thepolymer.

In aliphatic embodiments (from aliphatic isocyanate(s)), each R₁ groupcan include a linear aliphatic group, a branched aliphatic group, acycloaliphatic group, or combinations thereof. For instance, each R₁group can include a linear or branched alkylene group having from 3 to20 carbon atoms (e.g., an alkylene having from 4 to 15 carbon atoms, oran alkylene having from 6 to 10 carbon atoms), one or more cycloalkylenegroups having from 3 to 8 carbon atoms (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinationsthereof. The term “alkene” or “alkylene” as used herein refers to abivalent hydrocarbon. When used in association with the term C_(n) itmeans the alkene or alkylene group has “n” carbon atoms. For example,01-6 alkylene refers to an alkylene group having, e.g., 1, 2, 3, 4, 5,or 6 carbon atoms.

Examples of suitable aliphatic diisocyanates for producing thepolyurethane polymer chains include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate(H12MD1), diisocyanatododecane, lysine diisocyanate, and combinationsthereof.

The isocyanate-derived segments can include segments derived fromaliphatic diisocyanate. A majority of the isocyanate-derived segmentscan comprise segments derived from aliphatic diisocyanates. At least 90%of the isocyanate-derived segments are derived from aliphaticdiisocyanates. The isocyanate-derived segments can consist essentiallyof segments derived from aliphatic diisocyanates. The aliphaticdiisocyanate-derived segments can be derived substantially (e.g., about50 percent or more, about 60 percent or more, about 70 percent or more,about 80 percent or more, about 90 percent or more) from linearaliphatic diisocyanates. At least 80% of the aliphaticdiisocyanate-derived segments can be derived from aliphaticdiisocyanates that are free of side chains. The segments derived fromaliphatic diisocyanates can include linear aliphatic diisocyanateshaving from 2 to 10 carbon atoms.

When the isocyanate-derived segments are derived from aromaticisocyanate(s)), each R₁ group can include one or more aromatic groups,such as phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl,biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl. Unlessotherwise indicated, an aromatic group can be an unsubstituted aromaticgroup or a substituted aromatic group, and can also includeheteroaromatic groups. “Heteroaromatic” refers to monocyclic orpolycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ringsystems, where one to four ring atoms are selected from oxygen,nitrogen, or sulfur, and the remaining ring atoms are carbon, and wherethe ring system is joined to the remainder of the molecule by any of thering atoms. Examples of suitable heteroaryl groups include pyridyl,pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl,tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, furanyl,quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, andbenzothiazolyl groups.

Examples of suitable aromatic diisocyanates for producing thepolyurethane polymer chains include toluene diisocyanate (TDI), TDIadducts with trimethyloylpropane (TMP), methylene diphenyl diisocyanate(MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate(TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate,para-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyl diisocyanate (DBDI),4-chloro-1,3-phenylene diisocyanate, and combinations thereof. Thepolymer chains can be substantially free of aromatic groups.

The polyurethane polymer chains can be produced from diisocyanatesincluding HMDI, TDI, MDI, H12 aliphatics, and combinations thereof. Forexample, the polyurethane can comprise one or more polyurethane polymerchains produced from diisocyanates including HMDI, TDI, MDI, H12aliphatics, and combinations thereof.

Polyurethane chains which are at least partially crosslinked or whichcan be crosslinked, can be used in accordance with the presentdisclosure. It is possible to produce crosslinked or crosslinkablepolyurethane chains by reacting multi-functional isocyanates to form thepolyurethane. Examples of suitable triisocyanates for producing thepolyurethane chains include TDI, HDI, and IPDI adducts withtrimethyloylpropane (TMP), uretdiones (i.e., dimerized isocyanates),polymeric MDI, and combinations thereof.

The R₃ group in Formula 2 can include a linear or branched group havingfrom 2 to 10 carbon atoms, based on the particular chain extender polyolused, and can be, for example, aliphatic, aromatic, or an ether orpolyether. Examples of suitable chain extender polyols for producing thepolyurethane include ethylene glycol, lower oligomers of ethylene glycol(e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol),1,2-propylene glycol, 1,3-propylene glycol, lower oligomers of propyleneglycol (e.g., dipropylene glycol, tripropylene glycol, andtetrapropylene glycol), 1,4-butylene glycol, 2,3-butylene glycol,1,6-hexanediol, 1,8-octanediol, neopentyl glycol,1,4-cyclohexanedimethanol, 2-ethyl-1,6-hexanediol,1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylatedaromatic compounds (e.g., bis(2-hydroxyethyl) ethers of hydroquinone andresorcinol, xylene-a,a-diols, bis(2-hydroxyethyl) ethers ofxylene-a,a-diols, and combinations thereof.

The R₂ group in Formula 1 and 2 can include a polyether group, apolyester group, a polycarbonate group, an aliphatic group, or anaromatic group. Each R₂ group can be present in an amount of about 5percent to about 85 percent by weight, from about 5 percent to about 70percent by weight, or from about 10 percent to about 50 percent byweight, based on the total weight of the reactant monomers.

At least one R₂ group of the polyurethane includes a polyether segment(i.e., a segment having one or more ether groups). Suitable polyethergroups include, but are not limited to, polyethylene oxide (PEO),polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof. The term“alkyl” as used herein refers to straight chained and branched saturatedhydrocarbon groups containing one to thirty carbon atoms, for example,one to twenty carbon atoms, or one to ten carbon atoms. When used inassociation with the term O_(n) it means the alkyl group has “n” carbonatoms. For example, C₄ alkyl refers to an alkyl group that has 4 carbonatoms. C₁₋₇ alkyl refers to an alkyl group having a number of carbonatoms encompassing the entire range (i.e., 1 to 7 carbon atoms), as wellas all subgroups (e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7carbon atoms). Non-limiting examples of alkyl groups include, methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl(1,1- dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unlessotherwise indicated, an alkyl group can be an unsubstituted alkyl groupor a substituted alkyl group.

In some examples of the polyurethane, the at least one R₂ group includesa polyester group. The polyester group can be derived from thepolyesterification of one or more dihydric alcohols (e.g., ethyleneglycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol,1,3-butanediol, 2-methylpentanediol, 1,5,diethyleneglyco1,1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol,cyclohexanedimethanol, and combinations thereof) with one or moredicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid,suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaicacid, thiodipropionic acid and citraconic acid and combinationsthereof). The polyester group also can be derived from polycarbonateprepolymers, such as poly(hexamethylene carbonate) glycol,poly(propylene carbonate) glycol, poly(tetramethylene carbonate)glycol,and poly(nonanemethylene carbonate) glycol. Suitable polyesters caninclude, for example, polyethylene adipate (PEA), poly(l,4-butyleneadipate), poly(tetramethylene adipate), poly(hexamethylene adipate),polycaprolactone, polyhexamethylene carbonate, poly(propylenecarbonate), poly(tetramethylene carbonate), poly(nonanemethylenecarbonate), and combinations thereof.

At least one R₂ group can include a polycarbonate group. Thepolycarbonate group can be derived from the reaction of one or moredihydric alcohols (e.g., ethylene glycol, 1,3-propylene glycol,1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol,2-methylpentanediol, 1,5, diethylene glycol, 1,5-pentanediol,1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, andcombinations thereof) with ethylene carbonate.

The aliphatic group can be linear and can include, for example, analkylene chain having from 1 to 20 carbon atoms or an alkenylene chainhaving from 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene,butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, ethenylene, propenylene,butenylene, pentenylene, hexenylene, heptenylene, octenylene,nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). Theterm “alkene” or “alkylene” refers to a bivalent hydrocarbon. The term“alkenylene” refers to a bivalent hydrocarbon molecule or portion of amolecule having at least one double bond.

The aliphatic and aromatic groups can be substituted with one or morependant relatively hydrophilic and/or charged groups. The pendanthydrophilic group can include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9,10 or more) hydroxyl groups. The pendant hydrophilic group includes oneor more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) carboxylate groups. For example, thealiphatic group can include one or more polyacrylic acid group. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, thependant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7,8, 9, 10 or more) phosphate groups. In some examples, the pendanthydrophilic group includes one or more ammonium groups (e.g., tertiaryand/or quaternary ammonium). In other examples, the pendant hydrophilicgroup includes one or more zwitterionic groups (e.g., a betaine, such aspoly(carboxybetaine (pCB) and ammonium phosphonate groups such as aphosphatidylcholine group).

The R2 group can include charged groups that are capable of binding to acounterion to ionically crosslink the polymer and form ionomers. Forexample, R2 is an aliphatic or aromatic group having pendant amino,carboxylate, sulfonate, phosphate, ammonium, or zwitterionic groups, orcombinations thereof.

When a pendant hydrophilic group is present, the pendant hydrophilicgroup can be at least one polyether group, such as two polyether groups.In other cases, the pendant hydrophilic group is at least one polyester.The pendant hydrophilic group can be a polylactone group (e.g.,polyvinylpyrrolidone). Each carbon atom of the pendant hydrophilic groupcan optionally be substituted with, e.g., an alkyl group having from 1to 6 carbon atoms. The aliphatic and aromatic groups can be graftpolymeric groups, wherein the pendant groups are homopolymeric groups(e.g., polyether groups, polyester groups, polyvinylpyrrolidone groups).

The pendant hydrophilic group can be a polyether group (e.g., apolyethylene oxide (PEO) group, a polyethylene glycol (PEG) group), apolyvinylpyrrolidone group, a polyacrylic acid group, or combinationsthereof.

The pendant hydrophilic group can be bonded to the aliphatic group oraromatic group through a linker. The linker can be any bifunctionalsmall molecule (e.g., one having from 1 to 20 carbon atoms) capable oflinking the pendant hydrophilic group to the aliphatic or aromaticgroup. For example, the linker can include a diisocyanate group, aspreviously described herein, which when linked to the pendanthydrophilic group and to the aliphatic or aromatic group forms acarbamate bond. The linker can be 4,4′-diphenylmethane diisocyanate(MDI), as shown below.

The pendant hydrophilic group can be a polyethylene oxide group and thelinking group can be MDI, as shown below.

The pendant hydrophilic group can be functionalized to enable it to bondto the aliphatic or aromatic group, optionally through the linker. Forexample, when the pendant hydrophilic group includes an alkene group,which can undergo a Michael addition with a sulfhydryl-containingbifunctional molecule (i.e., a molecule having a second reactive group,such as a hydroxyl group or amino group), resulting in a hydrophilicgroup that can react with the polymer backbone, optionally through thelinker, using the second reactive group. For example, when the pendanthydrophilic group is a polyvinylpyrrolidone group, it can react with thesulfhydryl group on mercaptoethanol to result in hydroxyl-functionalizedpolyvinylpyrrolidone, as shown below.

At least one R₂ group in the polyurethane can include apolytetramethylene oxide group. At least one R₂ group of thepolyurethane can include an aliphatic polyol group functionalized with apolyethylene oxide group or polyvinylpyrrolidone group, such as thepolyols described in

E.P. Patent No. 2 462 908, which is hereby incorporated by reference.For example, the R₂ group can be derived from the reaction product of apolyol (e.g., pentaerythritol or 2,2,3-trihydroxypropanol) and eitherMDI-derivatized methoxypolyethylene glycol (to obtain compounds as shownin Formulas 6 or 7) or with MDI-derivatized polyvinylpyrrolidone (toobtain compounds as shown in Formulas 8 or 9) that had been previouslybeen reacted with mercaptoethanol, as shown below.

At least one R₂ of the polyurethane can be a polysiloxane, In thesecases, the R₂ group can be derived from a silicone monomer of Formula10, such as a silicone monomer disclosed in U.S. Pat. No. 5,969,076,which is hereby incorporated by reference:

wherein: a is 1 to 10 or larger (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or10); each R₄ independently is hydrogen, an alkyl group having from 1 to18 carbon atoms, an alkenyl group having from 2 to 18 carbon atoms,aryl, or polyether; and each R₅ independently is an alkylene grouphaving from 1 to 10 carbon atoms, polyether, or polyurethane.

Each R₄ group can independently be a H, an alkyl group having from 1 to10 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, anaryl group having from 1 to 6 carbon atoms, polyethylene, polypropylene,or polybutylene group. Each R₄ group can independently be selected fromthe group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, s-butyl, t-butyl, ethenyl, propenyl, phenyl, and polyethylenegroups.

Each R₅ group can independently include an alkylene group having from 1to 10 carbon atoms (e.g., a methylene, ethylene, propylene, butylene,pentylene, hexylene, heptylene, octylene, nonylene, or decylene group).Each R₅ group can be a polyether group (e.g., a polyethylene,polypropylene, or polybutylene group). Each R₅ group can be apolyurethane group.

Optionally, the polyurethane can include an at least partiallycrosslinked polymeric network that includes polymer chains that arederivatives of polyurethane. The level of crosslinking can be such thatthe polyurethane retains thermoplastic properties (i.e., the crosslinkedthermoplastic polyurethane can be melted and re-solidified under theprocessing conditions described herein). This crosslinked polymericnetwork can be produced by polymerizing one or more isocyanates with oneor more polyamino compounds, polysulfhydryl compounds, or combinationsthereof, as shown in Formulas 11 and 12, below:

wherein the variables are as described above. Additionally, theisocyanates can also be chain extended with one or more polyamino orpolythiol chain extenders to bridge two or more isocyanates, such aspreviously described for the polyurethanes of Formula 2.

The polyurethane chain can be physically crosslinked to anotherpolyurethane chain through e.g., nonpolar or polar interactions betweenthe urethane or carbamate groups of the polymers (the hard segments).The R₁ group in Formula 1, and the R₁ and R₃ groups in Formula 2, formthe portion of the polymer often referred to as the “hard segment”, andthe R₂ group forms the portion of the polymer often referred to as the“soft segment”. The soft segment is covalently bonded to the hardsegment. The polyurethane having physically crosslinked hard and softsegments can be a hydrophilic polyurethane (i.e., a polyurethane,including a thermoplastic polyurethane, including hydrophilic groups asdisclosed herein).

The polyurethane can be a thermoplastic polyurethane composed of MDI,PTMO, and 1,4-butylene glycol, as described in U.S. Pat. No. 4,523,005.Commercially available polyurethanes suitable for the present useinclude, but are not limited to those under the tradename “SANCURE”(e.g., the “SANCURE” series of polymer such as “SANCURE” 20025F) or“TECOPHILIC” (e.g., TG-500, TG-2000, SP-80A-150, SP-93A-100, SP-60D-60)(Lubrizol, Countryside, ll.L, USA), “PELLETHANE” 2355-85ATP and2355-95AE (Dow Chemical Company of Midland, Mich., USA.), “ESTANE”(e.g., ALR G 500, or 58213; Lubrizol, Countryside, Ill., USA).

One or more of the polyurethanes can be produced by polymerizing one ormore isocyanates with one or more polyols to produce copolymer chainshaving carbamate linkages (—N(C═O)O—) and one or more water-dispersibleenhancing moieties, where the polymer chain includes one or morewater-dispersible enhancing moieties (e.g., a monomer in polymer chain).The water-dispersible polyurethane can also be referred to as “awater-borne polyurethane polymer dispersion.” The water-dispersibleenhancing moiety can be added to the chain of Formula 1 or 2 (e.g.,within the chain and/or onto the chain as a side chain). Inclusion ofthe water-dispersible enhancing moiety enables the formation of awater-borne polyurethane dispersion. The term “water-borne” herein meansthe continuous phase of the dispersion or formulation of about 50 weightpercent to 100 weight percent water, about 60 weight percent to 100weight percent water, about 70 weight percent to 100 weight percentwater, or about 100 weight percent water. The term “water-bornedispersion” refers to a dispersion of a component (e.g., polymer,cross-linker, and the like) in water without co-solvents. The co-solventcan be used in the water-borne dispersion and the co-solvent can be anorganic solvent. Additional detail regarding the polymers,polyurethanes, isocyantes and the polyols are provided below.

The polyurethane (e.g., a water-borne polyurethane polymer dispersion)can include one or more water-dispersible enhancing moieties. Thewater-dispersible enhancing moiety can have at least one hydrophilic(e.g., poly(ethylene oxide)), ionic or potentially ionic group to assistdispersion of the polyurethane, thereby enhancing the stability of thedispersions. A water-dispersible polyurethane can be formed byincorporating a moiety bearing at least one hydrophilic group or a groupthat can be made hydrophilic (e.g., by chemical modifications such asneutralization) into the polymer chain. For example, these compounds canbe nonionic, anionic, cationic or zwitterionic or the combinationthereof. In one example, anionic groups such as carboxylic acid groupscan be incorporated into the chain in an inactive form and subsequentlyactivated by a salt-forming compound, such as a tertiary amine. Otherwater-dispersible enhancing moieties can also be reacted into thebackbone through urethane linkages or urea linkages, including lateralor terminal hydrophilic ethylene oxide or ureido units.

The water-dispersible enhancing moiety can be a one that includescarboxyl groups. Water-dispersible enhancing moiety that include acarboxyl group can be formed from hydroxy-carboxylic acids having thegeneral formula (HO)_(x)Q(COOH)_(y), where Q can be a straight orbranched bivalent hydrocarbon radical containing 1 to 12 carbon atoms,and x and y can each independently be 1 to 3. Illustrative examplesinclude dimethylolpropanoic acid (DMPA), dimethylol butanoic acid(DMBA), citric acid, tartaric acid, glycolic acid, lactic acid, malicacid, dihydroxymalic acid, dihydroxytartaric acid, and the like, andmixtures thereof.

The water-dispersible enhancing moiety can include reactive polymericpolyol components that contain pendant anionic groups that can bepolymerized into the backbone to impart water dispersiblecharacteristics to the polyurethane. Anionic functional polymericpolyols can include anionic polyester polyols, anionic polyetherpolyols, and anionic polycarbonate polyols, where additional detail isprovided in U.S. Pat. No. 5,334,690.

The water-dispersible enhancing moiety can include a side chainhydrophilic monomer. For example, the water-dispersible enhancing moietyincluding the side chain hydrophilic monomer can include alkylene oxidepolymers and copolymers in which the alkylene oxide groups have from2-10 carbon atoms as shown in U.S. Patent 6,897,281. Additional types ofwater-dispersible enhancing moieties can include thioglycolic acid,2,6-dihydroxybenzoic acid, sulfoisophthalic acid, polyethylene glycol,and the like, and mixtures thereof. Additional details regardingwater-dispersible enhancing moieties can be found in U.S. Pat. No.7,476,705.

Polyamides

The polymer can comprise a polyamide, such as a thermoplastic polyamide.The polyamide can be an elastomeric polyamide, including an elastomericthermoplastic polyamide. The polyamide can be a polyamide homopolymerhaving repeating polyamide segments of the same chemical structure.Alternatively, the polyamide can comprise a number of polyamide segmentshaving different polyamide chemical structures (e.g., polyamide 6segments, polyamide 11 segments, polyamide 12 segments, polyamide 66segments, etc.). The polyamide segments having different chemicalstructure can be arranged randomly, or can be arranged as repeatingblocks.

The polyamide can be a co-polyamide (i.e., a co-polymer includingpolyamide segments and non-polyamide segments). The polyamide segmentsof the co-polyamide can comprise or consist of polyamide 6 segments,polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, orany combination thereof. The polyamide segments of the co-polyamide canbe arranged randomly, or can be arranged as repeating segments. Thepolyamide segments can comprise or consist of polyamide 6 segments, orpolyamide 12 segments, or both polyamide 6 segment and polyamide 12segments. In the example where the polyamide segments of theco-polyamide include of polyamide 6 segments and polyamide 12 segments,the segments can be arranged randomly. The non-polyamide segments of theco-polyamide can comprise or consist of polyether segments, polyestersegments, or both polyether segments and polyester segments. Theco-polyamide can be a block co-polyamide, or can be a randomco-polyamide. The copolyamide can be formed from the polycondensation ofa polyamide oligomer or prepolymer with a second oligomer prepolymer toform a copolyamide (i.e., a co-polymer including polyamide segments.Optionally, the second prepolymer can be a hydrophilic prepolymer.

The polyamide can be a polyamide-containing block co-polymer. Forexample, the block co-polymer can have repeating hard segments, andrepeating soft segments. The hard segments can comprise polyamidesegments, and the soft segments can comprise non-polyamide segments. Thepolyamide-containing block co-polymer can be an elastomeric co-polyamidecomprising or consisting of polyamide-containing block co-polymershaving repeating hard segments and repeating soft segments. In blockco-polymers, including block co-polymers having repeating hard segmentsand soft segments, physical crosslinks can be present within thesegments or between the segments or both within and between thesegments.

The polyamide itself, or the polyamide segment of thepolyamide-containing block co-polymer can be derived from thecondensation of polyamide prepolymers, such as lactams, amino acids,and/or diamino compounds with dicarboxylic acids, or activated formsthereof. The resulting polyamide segments include amide linkages(—(CO)NH—). The term “amino acid” refers to a molecule having at leastone amino group and at least one carboxyl group. Each polyamide segmentof the polyamide can be the same or different.

The polyamide or the polyamide segment of the polyamide-containing blockco-polymer can be derived from the polycondensation of lactams and/oramino acids, and can include an amide segment having a structure shownin Formula 13, below, wherein R₆ group represents the portion of thepolyamide derived from the lactam or amino acid.

The R₆ group can be derived from a lactam. The R₆ group can be derivedfrom a lactam group having from 3 to 20 carbon atoms, or a lactam grouphaving from 4 to 15 carbon atoms, or a lactam group having from 6 to 12carbon atoms. The R₆ group can be derived from caprolactam orlaurolactam. The R₆ group can be derived from one or more amino acids.The R₆ group can be derived from an amino acid group having from 4 to 25carbon atoms, or an amino acid group having from 5 to 20 carbon atoms,or an amino acid group having from 8 to 15 carbon atoms. The R₆ groupcan be derived from 12-aminolauric acid or 11-aminoundecanoic acid.

Optionally, in order to increase the relative degree of hydrophilicityof the polyamide-containing block co-polymer, Formula 13 can include apolyamide-polyether block copolymer segment, as shown below:

wherein m is 3-20, and n is 1-8. Optionally, m is 4-15, or 6-12 (e.g.,6, 7, 8, 9, 10, 11, or 12), and n is 1, 2, or 3. For example, m can be11 or 12, and n can be 1 or 3. The polyamide or the polyamide segment ofthe polyamide-containing block co-polymer can be derived from thecondensation of diamino compounds with dicarboxylic acids, or activatedforms thereof, and can include an amide segment having a structure shownin Formula 15, below, wherein the R₇ group represents the portion of thepolyamide derived from the diamino compound, and the R₈ group representsthe portion derived from the dicarboxylic acid compound:

The R₇ group can be derived from a diamino compound that includes analiphatic group having from 4 to 15 carbon atoms, or from 5 to 10 carbonatoms, or from 6 to 9 carbon atoms. The diamino compound can include anaromatic group, such as phenyl, naphthyl, xylyl, and tolyl. Suitablediamino compounds from which the R₇ group can be derived include, butare not limited to, hexamethylene diamine (HMD), tetramethylene diamine,trimethyl hexamethylene diamine (TMD),m-xylylene diamine (MXD), and1,5-pentamine diamine. The R₈ group can be derived from a dicarboxylicacid or activated form thereof, including an aliphatic group having from4 to 15 carbon atoms, or from 5 to 12 carbon atoms, or from 6 to 10carbon atoms. The dicarboxylic acid or activated form thereof from whichR₈ can be derived includes an aromatic group, such as phenyl, naphthyl,xylyl, and tolyl groups. Suitable carboxylic acids or activated formsthereof from which R₈ can be derived include adipic acid, sebacic acid,terephthalic acid, and isophthalic acid. The polyamide chain can besubstantially free of aromatic groups.

Each polyamide segment of the polyamide (including thepolyamide-containing block co-polymer) can be independently derived froma polyamide prepolymer selected from the group consisting of12-aminolauric acid, caprolactam, hexamethylene diamine and adipic acid.

The polyamide can comprise or consist essentially of apoly(ether-block-amide). The poly(ether-block-amide) can be formed fromthe polycondensation of a carboxylic acid terminated polyamideprepolymer and a hydroxyl terminated polyether prepolymer to form apoly(ether-block-amide), as shown in Formula 16:

The poly(ether block amide) polymer can be prepared by polycondensationof polyamide blocks containing reactive ends with polyether blockscontaining reactive ends. Examples include: 1) polyamide blockscontaining diamine chain ends with polyoxyalkylene blocks containingcarboxylic chain ends; 2) polyamide blocks containing dicarboxylic chainends with polyoxyalkylene blocks containing diamine chain ends obtainedby cyanoethylation and hydrogenation of aliphatic dihydroxylatedalpha-omega polyoxyalkylenes known as polyether diols; 3) polyamideblocks containing dicarboxylic chain ends with polyether diols, theproducts obtained in this particular case being polyetheresteramides.The polyamide block of the poly(ether-block-amide) can be derived fromlactams, amino acids, and/or diamino compounds with dicarboxylic acidsas previously described. The polyether block can be derived from one ormore polyethers selected from the group consisting of polyethylene oxide(PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks comprising dicarboxylic chain ends derived from thecondensation of α, ω-aminocarboxylic acids, of lactams or ofdicarboxylic acids and diamines in the presence of a chain-limitingdicarboxylic acid. In poly(ether block amide) polymers of this type, aα, ω-aminocarboxylic acid such as aminoundecanoic acid can be used; alactam such as caprolactam or lauryllactam can be used; a dicarboxylicacid such as adipic acid, decanedioic acid or dodecanedioic acid can beused; and a diamine such as hexamethylenediamine can be used; or variouscombinations of any of the foregoing. The copolymer can comprisepolyamide blocks comprising polyamide 12 or of polyamide 6.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of one or more α,ω-aminocarboxylic acids and/or of one or more lactams containing from 6to 12 carbon atoms in the presence of a dicarboxylic acid containingfrom 4 to 12 carbon atoms, and are of low mass, i.e., they have anumber-average molecular weight of from 400 to 1000. In poly(ether blockamide) polymers of this type, an α, ω-aminocarboxylic acid such asaminoundecanoic acid or aminododecanoic acid can be used; a dicarboxylicacid such as adipic acid, sebacic acid, isophthalic acid, butanedioicacid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid, the sodium orlithium salt of sulphoisophthalic acid, dimerized fatty acids (thesedimerized fatty acids have a dimer content of at least 98 weight percentand are preferably hydrogenated) and dodecanedioic acidHOOC—(CH₂)₁₀—COOH can be used; and a lactam such as caprolactam andlauryllactam can be used; or various combinations of any of theforegoing. The copolymer can comprise polyamide blocks obtained bycondensation of lauryllactam in the presence of adipic acid ordodecanedioic acid and with a number average molecular weight of atleast 750 have a melting temperature of from about 127 to about 130degrees C. The various constituents of the polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., or from about 90 degrees C. to about 135 degrees C.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of at least one α,ω-aminocarboxylic acid (or a lactam), at least one diamine and at leastone dicarboxylic acid. In copolymers of this type, a α,ω-aminocarboxylicacid, the lactam and the dicarboxylic acid can be chosen from thosedescribed herein above and the diamine that can be used can include analiphatic diamine containing from 6 to 12 atoms and can be acyclicand/or saturated cyclic such as, but not limited to,hexamethylenediamine, piperazine, 1-aminoethylpiperazine,bisaminopropylpiperazine, tetramethylenediamine, octamethylene-diamine,decamethylenediamine, dodecamethylenediamine, 1,5-diaminohexane,2,2,4-trimethyl-1,6-diaminohexane, diamine polyols, isophoronediamine(IPD), methylpentamethylenediamine (MPDM), bis(aminocyclohexyl)methane(BACM) and bis(3-methyl-4-am inocyclohexyl)methane (BMACM).

The polyamide can be a thermoplastic polyamide and the constituents ofthe polyamide block and their proportion can be chosen in order toobtain a melting temperature of less than 150 degrees C., such as amelting point of from about 90 degrees C. to about 135 degrees C. Thevarious constituents of the thermoplastic polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., such as from about and 90 degrees C. to about 135degrees C.

The number average molar mass of the polyamide blocks can be from about300 grams per mole to about 15,000 grams per mole, from about 500 gramsper mole to about 10,000 grams per mole, from about 500 grams per moleto about 6,000 grams per mole, from about 500 grams per mole to about5,000 grams per mole, or from about 600 grams per mole to about 5,000grams per mole. The number average molecular weight of the polyetherblock can range from about 100 to about 6,000, from about 400 to about3000, or from about 200 to about 3,000. The polyether (PE) content (x)of the poly(ether block amide) polymer can be from about 0.05 to about0.8 (i.e., from about 5 mole percent to about 80 mole percent). Thepolyether blocks can be present in the polyamide in an amount of fromabout 10 weight percent to about 50 weight percent, from about 20 weightpercent to about 40 weight percent, or from about 30 weight percent toabout 40 weight percent. The polyamide blocks can be present in thepolyamide in an amount of from about 50 weight percent to about 90weight percent, from about 60 weight percent to about 80 weight percent,or from about 70 weight percent to about 90 weight percent.

The polyether blocks can contain units other than ethylene oxide units,such as, for example, propylene oxide or polytetrahydrofuran (whichleads to polytetramethylene glycol sequences). It is also possible touse simultaneously PEG blocks, i.e., those consisting of ethylene oxideunits, polypropylene glycol (PPG) blocks, i.e. those consisting ofpropylene oxide units, and poly(tetramethylene ether)glycol (PTMG)blocks, i.e. those consisting of tetramethylene glycol units, also knownas polytetrahydrofuran. PPG or PTMG blocks are advantageously used. Theamount of polyether blocks in these copolymers containing polyamide andpolyether blocks can be from about 10 weight percent to about 50 weightpercent of the copolymer, or from about 35 weight percent to about 50weight percent.

The copolymers containing polyamide blocks and polyether blocks can beprepared by any means for attaching the polyamide blocks and thepolyether blocks. In practice, two processes are essentially used, onebeing a 2-step process and the other a one-step process.

In the two-step process, the polyamide blocks having dicarboxylic chainends are prepared first, and then, in a second step, these polyamideblocks are linked to the polyether blocks. The polyamide blocks havingdicarboxylic chain ends are derived from the condensation of polyamideprecursors in the presence of a chain-stopper dicarboxylic acid. If thepolyamide precursors are only lactams or a,w-aminocarboxylic acids, adicarboxylic acid is added. If the precursors already comprise adicarboxylic acid, this is used in excess with respect to thestoichiometry of the diamines. The reaction usually takes place fromabout 180 to about 300 degrees C., such as from about 200 degrees toabout 290 degrees C., and the pressure in the reactor can be set fromabout 5 to about 30 bar and maintained for approximately 2 to 3 hours.The pressure in the reactor is slowly reduced to atmospheric pressureand then the excess water is distilled off, for example for one or twohours.

Once the polyamide having carboxylic acid end groups has been prepared,the polyether, the polyol and a catalyst are then added. The totalamount of polyether can be divided and added in one or more portions, ascan the catalyst. The polyether is added first and the reaction of theOH end groups of the polyether and of the polyol with the COOH endgroups of the polyamide starts, with the formation of ester linkages andthe elimination of water. Water is removed as much as possible from thereaction mixture by distillation and then the catalyst is introduced inorder to complete the linking of the polyamide blocks to the polyetherblocks. This second step takes place with stirring, preferably under avacuum of at least 50 millibar (5000 Pascals) at a temperature such thatthe reactants and the copolymers obtained are in the molten state. Byway of example, this temperature can be from about 100 to about 400degrees C., such as from about 200 to about 250 degrees C. The reactionis monitored by measuring the torque exerted by the polymer melt on thestirrer or by measuring the electric power consumed by the stirrer. Theend of the reaction is determined by the value of the torque or of thetarget power. The catalyst is defined as being any product whichpromotes the linking of the polyamide blocks to the polyether blocks byesterification. The catalyst can be a derivative of a metal (M) chosenfrom the group formed by titanium, zirconium and hafnium. The derivativecan be prepared from a tetraalkoxides consistent with the generalformula M(OR)₄, in which M represents titanium, zirconium or hafnium andR, which can be identical or different, represents linear or branchedalkyl radicals having from 1 to 24 carbon atoms.

The catalyst can comprise a salt of the metal (M), particularly the saltof (M) and of an organic acid and the complex salts of the oxide of (M)and/or the hydroxide of (M) and an organic acid. The organic acid can beformic acid, acetic acid, propionic acid, butyric acid, valeric acid,caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid,cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, maleic acid, fumaric acid, phthalic acid or crotonic acid. Theorganic acid can be an acetic acid or a propionic acid. M can bezirconium and such salts are called zirconyl salts, e.g., thecommercially available product sold under the name zirconyl acetate.

The weight proportion of catalyst can vary from about 0.01 to about 5percent of the weight of the mixture of the dicarboxylic polyamide withthe polyetherdiol and the polyol. The weight proportion of catalyst canvary from about 0.05 to about 2 percent of the weight of the mixture ofthe dicarboxylic polyamide with the polyetherdiol and the polyol.

In the one-step process, the polyamide precursors, the chain stopper andthe polyether are blended together; what is then obtained is a polymerhaving essentially polyether blocks and polyamide blocks of highlyvariable length, but also the various reactants that have reactedrandomly, which are distributed randomly along the polymer chain. Theyare the same reactants and the same catalyst as in the two-step processdescribed above. If the polyamide precursors are only lactams, it isadvantageous to add a little water. The copolymer has essentially thesame polyether blocks and the same polyamide blocks, but also a smallportion of the various reactants that have reacted randomly, which aredistributed randomly along the polymer chain. As in the first step ofthe two-step process described above, the reactor is closed and heated,with stirring. The pressure established is from about 5 to about 30 bar.When the pressure no longer changes, the reactor is put under reducedpressure while still maintaining vigorous stirring of the moltenreactants. The reaction is monitored as previously in the case of thetwo-step process.

The proper ratio of polyamide to polyether blocks can be found in asingle poly(ether block amide), or a blend of two or more differentcomposition poly(ether block amide)s can be used with the proper averagecomposition. It can be useful to blend a block copolymer having a highlevel of polyamide groups with a block copolymer having a higher levelof polyether blocks, to produce a blend having an average level ofpolyether blocks of about 20 to about 40 weight percent of the totalblend of poly(amid-block-ether) copolymers, or about 30 to about 35weight percent. The copolymer can comprise a blend of two differentpoly(ether-block-amide)s comprising at least one block copolymer havinga level of polyether blocks below 35 weight percent, and a secondpoly(ether-block-amide) having at least 45 weight percent of polyetherblocks.

Exemplary commercially available copolymers include, but are not limitedto, those available under the tradenames of “VESTAMID” (EvonikIndustries, Essen, Germany); “PLATAMID” (Arkema, Colombes, France),e.g., product code H2694; “PEBAX” (Arkema), e.g., product code “PEBAXMH1657” and “PEBAX MV1074”; “PEBAX RNEW” (Arkema); “GRILAMID”(EMS-Chemie AG, Domat-Ems, Switzerland), or also to other similarmaterials produced by various other suppliers.

The polyamide can be physically crosslinked through, e.g., nonpolar orpolar interactions between the polyamide groups of the polymers. Inexamples where the polyamide is a copolyamide, the copolyamide can bephysically crosslinked through interactions between the polyamidegroups, and optionally by interactions between the copolymer groups.When the co-polyamide is physically crosslinked through interactionsbetween the polyamide groups, the polyamide segments can form theportion of the polymer referred to as the hard segment, and copolymersegments can form the portion of the polymer referred to as the softsegment. For example, when the copolyamide is a poly(ether-block-amide),the polyamide segments form the hard segments of the polymer, andpolyether segments form the soft segments of the polymer. Therefore, insome examples, the polymer can include a physically crosslinkedpolymeric network having one or more polymer chains with amide linkages.

The polyamide segment of the co-polyamide can include polyamide-11 orpolyamide-12 and the polyether segment can be a segment selected fromthe group consisting of polyethylene oxide, polypropylene oxide, andpolytetramethylene oxide segments, and combinations thereof.

The polyamide can be partially or fully covalently crosslinked, aspreviously described herein. In some cases, the degree of crosslinkingpresent in the polyamide is such that, when it is thermally processed,e.g., in the form of a yarn or fiber to form the articles of the presentdisclosure, the partially covalently crosslinked thermoplastic polyamideretains sufficient thermoplastic character that the partially covalentlycrosslinked thermoplastic polyamide is melted during the processing andre-solidifies.

Polyesters

The polymers can comprise a polyester. The polyester can comprise athermoplastic polyester. Additionally, the polyester can be anelastomeric polyester, including a thermoplastic polyester. Thepolyester can be formed by reaction of one or more carboxylic acids, orits ester-forming derivatives, with one or more bivalent or multivalentaliphatic, alicyclic, aromatic or araliphatic alcohols or a bisphenol.The polyester can be a polyester homopolymer having repeating polyestersegments of the same chemical structure. Alternatively, the polyestercan comprise a number of polyester segments having different polyesterchemical structures (e.g., polyglycolic acid segments, polylactic acidsegments, polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, etc.). The polyester segments havingdifferent chemical structure can be arranged randomly, or can bearranged as repeating blocks.

Exemplary carboxylic acids that can be used to prepare a polyesterinclude, but are not limited to, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decanedicarboxylic acid, undecane dicarboxylic acid, terephthalic acid,isophthalic acid, alkyl-substituted or halogenated terephthalic acid,alkyl-substituted or halogenated isophthalic acid, nitro-terephthalicacid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl thioetherdicarboxylic acid, 4,4′-diphenyl sulfone-dicarboxylic acid,4,4′-diphenyl alkylenedicarboxylic acid, naphthalene-2,6-dicarboxylicacid, cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylicacid. Exemplary diols or phenols suitable for the preparation of thepolyester include, but are not limited to, ethylene glycol, diethyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol,1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol,2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol,1,4-cyclohexane dimethanol, and bis-phenol A.

The polyester can be a polybutylene terephthalate (PBT), apolytrimethylene terephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), a liquid crystal polyester, or a blendor mixture of two or more of the foregoing.

The polyester can be a co-polyester (i.e., a co-polymer includingpolyester segments and non-polyester segments). The co-polyester can bean aliphatic co-polyester (i.e., a co-polyester in which both thepolyester segments and the non-polyester segments are aliphatic).Alternatively, the co-polyester can include aromatic segments. Thepolyester segments of the co-polyester can comprise or consistessentially of polyglycolic acid segments, polylactic acid segments,polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, or any combination thereof. The polyestersegments of the co-polyester can be arranged randomly, or can bearranged as repeating blocks.

For example, the polyester can be a block co-polyester having repeatingblocks of polymeric units of the same chemical structure which arerelatively harder (hard segments), and repeating blocks of the samechemical structure which are relatively softer (soft segments). In blockco-polyesters, including block co-polyesters having repeating hardsegments and soft segments, physical crosslinks can be present withinthe blocks or between the blocks or both within and between the blocks.The polymer can comprise or consist essentially of an elastomericco-polyester having repeating blocks of hard segments and repeatingblocks of soft segments.

The non-polyester segments of the co-polyester can comprise or consistessentially of polyether segments, polyamide segments, or both polyethersegments and polyamide segments. The co-polyester can be a blockco-polyester, or can be a random co-polyester. The co-polyester can beformed from the polycondensation of a polyester oligomer or prepolymerwith a second oligomer prepolymer to form a block copolyester.Optionally, the second prepolymer can be a hydrophilic prepolymer. Forexample, the co-polyester can be formed from the polycondensation ofterephthalic acid or naphthalene dicarboxylic acid with ethylene glycol,1,4-butanediol, or 1,3-propanediol. Examples of co-polyesters includepolyethylene adipate, polybutylene succinate,poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene terephthalate,polybutylene terephthalate, polytrimethylene terephthalate, polyethylenenapthalate, and combinations thereof. The co-polyamide can comprise orconsist of polyethylene terephthalate.

The polyester can be a block copolymer comprising segments of one ormore of polybutylene terephthalate (PBT), a polytrimethyleneterephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), and a liquid crystal polyester. Forexample, a suitable polyester that is a block copolymer can be a PET/PEIcopolymer, a polybutylene terephthalate/tetraethylene glycol copolymer,a polyoxyalkylenediimide diacid/polybutylene terephthalate copolymer, ora blend or mixture of any of the foregoing.

The polyester can be a biodegradable resin, for example, a copolymerizedpolyester in which poly(a-hydroxy acid) such as polyglycolic acid orpolylactic acid is contained as principal repeating units.

The disclosed polyesters can be prepared by a variety ofpolycondensation methods known to the skilled artisan, such as a solventpolymerization or a melt polymerization process.

Polyolefins

The polymers can comprise or consist essentially of a polyolefin. Thepolyolefin can be a thermoplastic polyolefin. Additionally, thepolyolefin can be an elastomeric polyolefin, including a thermoplasticelastomeric polyolefin. Exemplary polyolefins can include polyethylene,polypropylene, and olefin elastomers (e.g., metallocene-catalyzed blockcopolymers of ethylene and a-olefins having 4 to about 8 carbon atoms).The polyolefin can be a polymer comprising a polyethylene, anethylene-α-olefin copolymer, an ethylene-propylene rubber (EPDM), apolybutene, a polyisobutylene, a poly-4-methylpent-1-ene, apolyisoprene, a polybutadiene, a ethylene-methacrylic acid copolymer,and an olefin elastomer such as a dynamically cross-linked polymerobtained from polypropylene (PP) and an ethylene-propylene rubber(EPDM), and blends or mixtures of the foregoing. Further exemplarypolyolefins include polymers of cycloolefins such as cyclopentene ornorbornene.

It is to be understood that polyethylene, which optionally can becrosslinked, is inclusive a variety of polyethylenes, including lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE), medium density polyethylene (MDPE), high densitypolyethylene (HDPE), high density and high molecular weight polyethylene(HDPE-HMW), high density and ultrahigh molecular weight polyethylene(HDPE-UHMVV), and blends or mixtures of any the foregoing polyethylenes.A polyethylene can also be a polyethylene copolymer derived frommonomers of monolefins and diolefins copolymerized with a vinyl, acrylicacid, methacrylic acid, ethyl acrylate, vinyl alcohol, and/or vinylacetate. Polyolefin copolymers comprising vinyl acetate-derived unitscan be a high vinyl acetate content copolymer, e.g., greater than about50 weight percent vinyl acetate-derived composition.

The polyolefin can be formed through free radical, cationic, and/oranionic polymerization by methods well known to those skilled in the art(e.g., using a peroxide initiator, heat, and/or light). The disclosedpolyolefin can be prepared by radical polymerization under high pressureand at elevated temperature. Alternatively, the polyolefin can beprepared by catalytic polymerization using a catalyst that normallycontains one or more metals from group IVb, Vb, VIb or VIII metals. Thecatalyst usually has one or more than one ligand, typically oxides,halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/oraryls that can be either p- or s-coordinated complexed with the groupIVb, Vb, VIb or VIII metal. The metal complexes can be in the free formor fixed on substrates, typically on activated magnesium chloride,titanium(III) chloride, alumina or silicon oxide. The metal catalystscan be soluble or insoluble in the polymerization medium. The catalystscan be used by themselves in the polymerization or further activatorscan be used, typically a group Ia, IIa and/or IIIa metal alkyls, metalhydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes.The activators can be modified conveniently with further ester, ether,amine or silyl ether groups.

Suitable polyolefins can be prepared by polymerization of monomers ofmonolefins and diolefins as described herein. Exemplary monomers thatcan be used to prepare the polyolefin include, but are not limited to,ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene,3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixturesthereof.

Suitable ethylene-a-olefin copolymers can be obtained bycopolymerization of ethylene with an a-olefin such as propylene,butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like havingcarbon numbers of 3 to 12.

Suitable dynamically cross-linked polymers can be obtained bycross-linking a rubber component as a soft segment while at the sametime physically dispersing a hard segment such as PP and a soft segmentsuch as EPDM by using a kneading machine such as a Banbury mixer and abiaxial extruder.

The polyolefin can be a mixture of polyolefins, such as a mixture of twoor more polyolefins disclosed herein above. For example, a suitablemixture of polyolefins can be a mixture of polypropylene withpolyisobutylene, polypropylene with polyethylene (for example PP/HDPE,PP/LDPE) or mixtures of different types of polyethylene (for exampleLDPE/HDPE).

The polyolefin can be a copolymer of suitable monolefin monomers or acopolymer of a suitable monolefin monomer and a vinyl monomer. Exemplarypolyolefin copolymers include ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

The polyolefin can be a polypropylene homopolymer, a polypropylenecopolymers, a polypropylene random copolymer, a polypropylene blockcopolymer, a polyethylene homopolymer, a polyethylene random copolymer,a polyethylene block copolymer, a low density polyethylene (LDPE), alinear low density polyethylene (LLDPE), a medium density polyethylene,a high density polyethylene (HDPE), or blends or mixtures of one or moreof the preceding polymers.

The polyolefin can be a polypropylene. The term “polypropylene,” as usedherein, is intended to encompass any polymeric composition comprisingpropylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as ethylene, butylene, and the like). Such a term also encompassesany different configuration and arrangement of the constituent monomers(such as atactic, syndiotactic, isotactic, and the like). Thus, the termas applied to fibers is intended to encompass actual long strands,tapes, threads, and the like, of drawn polymer. The polypropylene can beof any standard melt flow (by testing); however, standard fiber gradepolypropylene resins possess ranges of Melt Flow Indices between about 1and 1000.

The polyolefin can be a polyethylene. The term “polyethylene,” as usedherein, is intended to encompass any polymeric composition comprisingethylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as propylene, butylene, and the like). Such a term alsoencompasses any different configuration and arrangement of theconstituent monomers (such as atactic, syndiotactic, isotactic, and thelike). Thus, the term as applied to fibers is intended to encompassactual long strands, tapes, threads, and the like, of drawn polymer. Thepolyethylene can be of any standard melt flow (by testing); however,standard fiber grade polyethylene resins possess ranges of Melt FlowIndices between about 1 and 1000.

The thermoplastic material can further comprise one or more processingaids. The processing aid can be a non-polymeric material. Theseprocessing aids can be independently selected from the group including,but not limited to, curing agents, initiators, plasticizers, moldrelease agents, lubricants, antioxidants, flame retardants, dyes,pigments, reinforcing and non-reinforcing fillers, fiber reinforcements,and light stabilizers.

In accordance with an aspect, a method of making the polymer-based itemincludes disposing (e.g., affixing) an optical element onto a firstsurface of polymer-based item or melting the structurally coloredarticle and the like, the first surface of the article defined by afirst polymeric material (e.g., a first thermoplastic material). As aresult, the optical element, as disposed on the first surface, imparts astructural color to the polymer-based item.

In some aspects, the first polymeric material can be a thermoplasticmaterial, and the optical element is disposed onto the thermoplasticmaterial. In general, a thermoplastic polymer softens or melts whenheated and returns to a solid state when cooled. The thermoplasticpolymer transitions from a solid state to a softened state or liquidstate when heated to or above one or more of the: (1) creep relaxationtemperature (T_(cr)), (2) Vicat softening temperature (T_(vs)), (3) heatdeflection temperature (T_(hd)), or (4) melting temperature (T_(m)).When sufficiently cooled, the thermoplastic polymer transitions from thesoftened or liquid state to the solid state. As such, the thermoplasticpolymer may be softened or melted, molded, cooled, re-softened orre-melted, re-molded, and cooled again through multiple cycles.

In an aspect, the method involves increasing a temperature of at least aportion of the first surface of the article to a first temperature at orabove one or more of the: (1) creep relaxation temperature, (2) Vicatsoftening temperature, (3) heat deflection temperature, or (4) meltingtemperature, of the first thermoplastic material. The optical elementcan be disposed on the first thermoplastic material while thetemperature is at or above the first temperature. In another aspect, thetemperature can be lowered to a second temperature that is below one ormore of: (1) creep relaxation temperature, (2) Vicat softeningtemperature, (3) heat deflection temperature, or (4) meltingtemperature, of the first thermoplastic material, to at least partiallyre-solidify the first thermoplastic material, and the optical element isdisposed on the first thermoplastic material while the temperature is ator below the second temperature.

In some aspects, the method includes increasing a temperature of the atleast a portion of the first surface of the article to a firsttemperature at or above one of a creep relaxation temperature, a heatdeflection temperature, a Vicat softening temperature, or a meltingtemperature of the first thermoplastic material. Then the texture of theat least a portion of the first surface can be altered while thetemperature of the first surface is at or above the first temperature.Subsequently, the optical element can be disposed onto at the at least aportion of the first surface having the altered texture.

Altering the texture of the first surface can include, for example,contacting a transfer medium having a first textured surface with thefirst surface of the article during or after increasing the temperatureof the first surface of the article to the first temperature; and usingthe first textured surface of the transfer medium, forming a secondtextured surface on the first surface of the article prior to disposingthe optical element onto the first surface. In various aspects, thefirst textured surface of the transfer medium is an inverse or a reliefof the resulting textured surface on the article. The transfer mediumused to alter the texture of the surface can include a release paper, amold, a drum, a plate, or a roller. In these aspects, the combination ofthe textured surface and optical element can impart the structural colorto the article.

In various aspects, disposing an optical element on the first surface ofthe article can include forming or depositing the optical element on thefirst surface of the article, including, for example, depositing theoptical element using a technique comprising: physical vapor deposition,electron beam deposition, atomic layer deposition, molecular beamepitaxy, cathodic arc deposition, pulsed laser deposition, sputtering,chemical vapor deposition, plasma-enhanced chemical vapor deposition,low pressure chemical vapor deposition, wet chemistry techniques, orcombinations thereof. Disposing the optical element can further includeoptionally depositing at least three layers of the optical element usinga deposition process, optionally depositing a first layer comprising ametal, optionally depositing a second layer comprising a metal oxide,optionally depositing both a first layer comprising a metal and a secondlayer comprising a metal oxide, or a combination thereof. The optionalfirst layer can comprise a titanium layer, or a silicon layer, and theoptional second layer can comprise a titanium dioxide layer or a silicondioxide layer.

According to the various embodiments, a textured surface (e.g., texturedlayer, textured structure) can be formed or provided, and thecombination of the textured surface and the optical element impart thestructural color to the article.

As described in some detail above in reference to SC filament, textiles,filaments, fibers, and yarns are descried in more detail, where some ofthe discussion is directed to other types of filaments or fibers whichcan be used in conjunction with the SC filament. A “textile” may bedefined as any material manufactured from fibers, filaments, or yarnscharacterized by flexibility, fineness, and a high ratio of length tothickness. Textiles generally fall into two categories. The firstcategory includes textiles produced directly from webs of filaments orfibers by randomly interlocking to construct non-woven fabrics andfelts. The second category includes textiles formed through a mechanicalmanipulation of yarn, thereby producing a woven fabric, a knittedfabric, a braided fabric, a crocheted fabric, and the like. The yarns,fibers, and articles of manufacture can include SC filaments of thepresent disclosure as well as other filaments, fibers, and yarns.

The terms “filament,” “fiber,” or “fibers” refer to materials that arein the form of discrete elongated pieces that are significantly longerthan they are wide. The fiber can include natural, manmade or syntheticfibers. The fibers may be produced by conventional techniques, such asextrusion, electrospinning, interfacial polymerization, pulling, and thelike. The fibers can include carbon fibers, boron fibers, siliconcarbide fibers, titania fibers, alumina fibers, quartz fibers, glassfibers, such as E, A, C, ECR, R, S, D, and NE glasses and quartz, or thelike. The fibers can be fibers formed from synthetic polymers capable offorming fibers such as poly(ether ketone), polyimide, polybenzoxazole,poly(phenylene sulfide), polyesters, polyolefins (e.g., polyethylene,polypropylene), aromatic polyamides (e.g., an aramid polymer such aspara-aramid fibers and meta-aramid fibers), aromatic polyimides,polybenzimidazoles, polyetherimides, polytetrafluoroethylene, acrylic,modacrylic, poly(vinyl alcohol), polyamides, polyurethanes, andcopolymers such as polyether-polyurea copolymers,polyester-polyurethanes, polyether block amide copolymers, or the like.The fibers can be natural fibers (e.g., silk, wool, cashmere, vicuna,cotton, flax, hemp, jute, sisal). The fibers can be man-made fibers fromregenerated natural polymers, such as rayon, lyocell, acetate,triacetate, rubber, and poly(lactic acid).

The fibers can have an indefinite length. For example, man-made andsynthetic fibers are generally extruded in substantially continuousstrands. Alternatively, the fibers can be staple fibers, such as, forexample, cotton fibers or extruded synthetic polymer fibers can be cutto form staple fibers of relatively uniform length. The staple fiber canhave a have a length of about 1 millimeter to 100 centimeters or more aswell as any increment therein (e.g., 1 millimeter increments).

The fiber can have any of a variety of cross-sectional shapes. Naturalfibers can have a natural cross-section, or can have a modifiedcross-sectional shape (e.g., with processes such as mercerization).Man-made or synthetic fibers can be extruded to provide a strand havinga predetermined cross-sectional shape. The cross-sectional shape of afiber can affect properties, such as its softness, luster, and wickingability. The fibers can have round or essentially round cross sections.Alternatively, the fibers can have non-round cross sections, such asflat, oval, octagonal, rectangular, wedge-shaped, triangular, dog-bone,multi-lobal, multi-channel, hollow, core-shell, or other shapes.

The fiber can be processed. For example, the properties of fibers can beaffected, at least in part, by processes such as drawing (stretching)the fibers, annealing (hardening) the fibers, and/or crimping ortexturizing the fibers.

In some cases a fiber can be a multi-component fiber, such as onecomprising two or more co-extruded polymeric materials. The two or moreco-extruded polymeric materials can be extruded in a core-sheath,islands-in-the-sea, segmented-pie, striped, or side-by-sideconfiguration. A multi-component fiber can be processed in order to forma plurality of smaller fibers (e.g., microfibers) from a single fiber,for example, by remove a sacrificial material.

The fiber can be a carbon fiber such as TARIFYL produced by FormosaPlastics Corp. of Kaohsiung City, Taiwan, (e.g., 12,000, 24,000, and48,000 fiber tows, specifically fiber types TC-35 and TC-35R), carbonfiber produced by SGL Group of Wiesbaden, Germany (e.g., 50,000 fibertow), carbon fiber produced by Hyosung of Seoul, South Korea, carbonfiber produced by Toho Tenax of Tokyo, Japan, fiberglass produced byJushi Group Co., LTD of Zhejiang, China (e.g., E6, 318, silane-basedsizing, filament diameters 14, 15, 17, 21,and 24 micrometers), andpolyester fibers produced by Amann Group of Bonningheim, Germany (e.g.,SERAFILE 200/2 non-lubricated polyester filament and SERAFILE COMPHIL200/2 lubricated polyester filament).

A plurality of fibers includes 2 to hundreds or thousands or morefibers. The plurality of fibers can be in the form of bundles of strandsof fibers, referred to as tows, or in the form of relatively alignedstaple fibers referred to as sliver and roving. A single type fiber canbe used either alone or in combination with one or more different typesof fibers by co-mingling two or more types of fibers. Examples ofco-mingled fibers include polyester fibers with cotton fibers, glassfibers with carbon fibers, carbon fibers with aromatic polyimide(aramid) fibers, and aromatic polyimide fibers with glass fibers.

As used herein, the term “yarn” refers to an assembly formed of one ormore fibers, wherein the strand has a substantial length and arelatively small cross-section, and is suitable for use in theproduction of textiles by hand or by machine, including textiles madeusing weaving, knitting, crocheting, braiding, sewing, embroidery, orropemaking techniques. Thread is a type of yarn commonly used forsewing.

Yarns can be made using fibers formed of natural, man-made and syntheticmaterials. Synthetic fibers are most commonly used to make spun yarnsfrom staple fibers, and filament yarns. Spun yarn is made by arrangingand twisting staple fibers together to make a cohesive strand. Theprocess of forming a yarn from staple fibers typically includes cardingand drawing the fibers to form sliver, drawing out and twisting thesliver to form roving, and spinning the roving to form a strand.Multiple strands can be plied (twisted together) to make a thicker yarn.The twist direction of the staple fibers and of the plies can affect thefinal properties of the yarn. A filament yarn can be formed of a singlelong, substantially continuous filament, which is conventionallyreferred to as a “monofilament yarn,” or a plurality of individualfilaments grouped together. A filament yarn can also be formed of two ormore long, substantially continuous filaments which are grouped togetherby grouping the filaments together by twisting them or entangling themor both. As with staple yarns, multiple strands can be plied together toform a thicker yarn.

Once formed, the yarn can undergo further treatment such as texturizing,thermal or mechanical treating, or coating with a material such as asynthetic polymer. The fibers, yarns, or textiles, or any combinationthereof, used in the disclosed articles can be sized. Sized fibers,yarns, and/or textiles are coated on at least part of their surface witha sizing composition selected to change the absorption or wearcharacteristics, or for compatibility with other materials. The sizingcomposition facilitates wet-out and wet-through of the coating or resinupon the surface and assists in attaining desired physical properties inthe final article. An exemplary sizing composition can comprise, forexample, epoxy polymers, urethane-modified epoxy polymers, polyesterpolymers, phenol polymers, polyamide polymers, polyurethane polymers,polycarbonate polymers, polyetherimide polymers, polyamideimidepolymers, polystylylpyridine polymers, polyimide polymers bismaleimidepolymers, polysulfone polymers, polyethersulfone polymers,epoxy-modified urethane polymers, polyvinyl alcohol polymers, polyvinylpyrrolidone polymers, and mixtures thereof.

Two or more yarns can be combined, for example, to form composite yarnssuch as single- or double-covered yarns, and corespun yarns.Accordingly, yarns may have a variety of configurations that generallyconform to the descriptions provided herein.

The yarn can comprise at least one thermoplastic material (e.g., one ormore of the fibers can be made of thermoplastic material). The yarn canbe made of a thermoplastic material. The yarn can be coated with a layerof a material such as a thermoplastic material.

The linear mass density or weight per unit length of a yarn can beexpressed using various units, including denier (D) and tex. Denier isthe mass in grams of 9000 meters of yarn. The linear mass density of asingle filament of a fiber can also be expressed using denier perfilament (DPF). Tex is the mass in grams of a 1000 meters of yarn.Decitex is another measure of linear mass and is the mass in grams for a10,000 meters of yarn.

As used herein, tenacity is understood to refer to the amount of force(expressed in units of weight, for example: pounds, grams, centinewtonsor other units) needed to break a yarn (i.e., the breaking force orbreaking point of the yarn), divided by the linear mass density of theyarn expressed, for example, in (unstrained) denier, decitex, or someother measure of weight per unit length. The breaking force of the yarnis determined by subjecting a sample of the yarn to a known amount offorce, for example, using a strain gauge load cell such as an INSTRONbrand testing system (Norwood, Mass., USA). Yarn tenacity and yarnbreaking force are distinct from burst strength or bursting strength ofa textile, which is a measure of how much pressure can be applied to thesurface of a textile before the surface bursts.

Generally, in order for a yarn to withstand the forces applied in anindustrial knitting machine, the minimum tenacity required isapproximately 1.5 grams per Denier. Most yarns formed from commoditypolymeric materials generally have tenacities in the range of about 1.5grams per Denier to about 4 grams per Denier. For example, polyesteryarns commonly used in the manufacture of knit uppers for footwear havetenacities in the range of about 2.5 to about 4 grams per Denier. Yarnsformed from commodity polymeric materials which are considered to havehigh tenacities generally have tenacities in the range of about 5 gramsper Denier to about 10 grams per Denier. For example, commerciallyavailable package dyed polyethylene terephthalate yarn from NationalSpinning (Washington, N.C., USA) has a tenacity of about 6 grams perDenier, and commercially available solution dyed polyethyleneterephthalate yarn from Far Eastern New Century (Taipei, Taiwan) has atenacity of about 7 grams per Denier. Yarns formed from high performancepolymeric materials generally have tenacities of about 11 grams perDenier or greater. For example, yarns formed of aramid fiber typicallyhave tenacities of about 20 grams per Denier, and yarns formed ofultra-high molecular weight polyethylene (UHMWPE) having tenacitiesgreater than 30 grams per Denier are available from Dyneema (Stanley,N.C., USA) and Spectra (Honeywell-Spectra, Colonial Heights, Va., USA).

Various techniques exist for mechanically manipulating yarns to form atextile. Such techniques include, for example, interweaving,intertwining and twisting, and interlooping. Interweaving is theintersection of two yarns that cross and interweave at right angles toeach other. The yarns utilized in interweaving are conventionallyreferred to as “warp” and “weft.” A woven textile includes include awarp yarn and a weft yarn. The warp yarn extends in a first direction,and the weft strand extends in a second direction that is substantiallyperpendicular to the first direction. Intertwining and twistingencompasses various procedures, such as braiding and knotting, whereyarns intertwine with each other to form a textile. Interloopinginvolves the formation of a plurality of columns of intermeshed loops,with knitting being the most common method of interlooping. The textilemay be primarily formed from one or more yarns that aremechanically-manipulated, for example, through interweaving,intertwining and twisting, and/or interlooping processes, as mentionedabove.

The textile can be a nonwoven textile. Generally, a nonwoven textile orfabric is a sheet or web structure made from fibers and/or yarns thatare bonded together. The bond can be a chemical and/or mechanical bond,and can be formed using heat, solvent, adhesive or a combinationthereof. Exemplary nonwoven fabrics are flat or tufted porous sheetsthat are made directly from separate fibers, molten plastic and/orplastic film. They are not made by weaving or knitting and do notnecessarily require converting the fibers to yarn, although yarns can beused as a source of the fibers. Nonwoven textiles are typicallymanufactured by putting small fibers together in the form of a sheet orweb (similar to paper on a paper machine), and then binding them eithermechanically (as in the case of felt, by interlocking them with serratedor barbed needles, or hydro-entanglement such that the inter-fiberfriction results in a stronger fabric), with an adhesive, or thermally(by applying binder (in the form of powder, paste, or polymer melt) andmelting the binder onto the web by increasing temperature). A nonwoventextile can be made from staple fibers (e.g., from wetlaid, airlaid,carding/crosslapping processes), or extruded fibers (e.g., frommeltblown or spunbond processes, or a combination thereof), or acombination thereof. Bonding of the fibers in the nonwoven textile canbe achieved with thermal bonding (with or without calendering),hydro-entanglement, ultrasonic bonding, needlepunching (needlefelting),chemical bonding (e.g., using binders such as latex emulsions orsolution polymers or binder fibers or powders), meltblown bonding (e.g.,fiber is bonded as air attenuated fibers intertangle during simultaneousfiber and web formation).

Now having described embodiments of the disclosure, evaluation ofvarious properties and characteristics described herein are by varioustesting procedures as described herein below.

Method to Determine the Melting Temperature, and Glass TransitionTemperature. The melting temperature and glass transition temperatureare determined using a commercially available Differential Scanningcalorimeter (“DSC”) in accordance with ASTM D3418-97. Briefly, a 10-15gram sample is placed into an aluminum DSC pan and then the lead wassealed with the crimper press. The DSC is configured to scan from -100degrees C. to 225 degrees C. with a 20 degrees C./minute heating rate,hold at 225 degrees C. for 2 minutes, and then cool down to 25 degreesC. at a rate of −10 degrees C./minute. The DSC curve created from thisscan is then analyzed using standard techniques to determine the glasstransition temperature and the melting temperature.

Method to Determine the Melt Flow Index. The melt flow index isdetermined according to the test method detailed in ASTM D1238-13Standard Test Method for Melt Flow Rates of Thermoplastics by ExtrusionPlastometer, using Procedure A described therein. Briefly, the melt flowindex measures the rate of extrusion of thermoplastics through anorifice at a prescribed temperature and load. In the test method,approximately 7 grams of the material is loaded into the barrel of themelt flow apparatus, which has been heated to a temperature specifiedfor the material. A weight specified for the material is applied to aplunger and the molten material is forced through the die. A timedextrudate is collected and weighed. Melt flow rate values are calculatedin grams/10 min.

Method to Determine the Creep Relation Temperature T_(cr). The creeprelation temperature T_(cr) is determined according to the exemplarytechniques described in U.S. Pat. No. 5,866,058. The creep relaxationtemperature T_(cr) is calculated to be the temperature at which thestress relaxation modulus of the tested material is 10% relative to thestress relaxation modulus of the tested material at the solidificationtemperature of the material, where the stress relaxation modulus ismeasured according to ASTM E328-02. The solidification temperature isdefined as the temperature at which there is little to no change in thestress relaxation modulus or little to no creep about 300 seconds aftera stress is applied to a test material, which can be observed byplotting the stress relaxation modulus (in Pa) as a function oftemperature (in ° C.).

Method to Determine the Vicat Softening Temperature T_(vs). The Vicatsoftening temperature T_(vs) is be determined according to the testmethod detailed in ASTM D1525-09 Standard Test Method for VicatSoftening Temperature of Plastics, preferably using Load A and Rate A.Briefly, the Vicat softening temperature is the temperature at which aflat-ended needle penetrates the specimen to the depth of 1 mm under aspecific load. The temperature reflects the point of softening expectedwhen a material is used in an elevated temperature application. It istaken as the temperature at which the specimen is penetrated to a depthof 1 mm by a flat-ended needle with a 1 mm² circular or squarecross-section. For the Vicat A test, a load of 10 N is used, whereas forthe Vicat B test, the load is 50 N. The test involves placing a testspecimen in the testing apparatus so that the penetrating needle restson its surface at least 1 mm from the edge. A load is applied to thespecimen per the requirements of the Vicat A or Vicat B test. Thespecimen is then lowered into an oil bath at 23° C. The bath is raisedat a rate of 50° C. or 120° C. per hour until the needle penetrates 1mm. The test specimen must be between 3 and 6.5 mm thick and at least 10mm in width and length. No more than three layers can be stacked toachieve minimum thickness.

Method to Determine the Heat Deflection Temperature Thd. The heatdeflection temperature Thd is be determined according to the test methoddetailed in ASTM D648-16 Standard Test Method for Deflection Temperatureof Plastics Under Flexural Load in the Edgewise Position, using a 0.455MPa applied stress. Briefly, the heat deflection temperature is thetemperature at which a polymer or plastic sample deforms under aspecified load. This property of a given plastic material is applied inmany aspects of product design, engineering, and manufacture of productsusing thermoplastic components. In the test method, the bars are placedunder the deflection measuring device and a load (0.455 MPa) of isplaced on each specimen. The specimens are then lowered into a siliconeoil bath where the temperature is raised at 2° C. per minute until theydeflect 0.25 mm per ASTM D648-16. ASTM uses a standard bar 5″×½″×¼″. ISOedgewise testing uses a bar 120 mm×10 mm×4 mm. ISO flatwise testing usesa bar 80 mm×10 mm×4 mm.

Transmittance and reflectance. Measurements for visible lighttransmittance and visible light reflectance were performed using aShimadzu UV-2600 Spectrometer (Shimadzu Corporation, Japan). Thespectrometer was calibrated using a standard prior to the measurements.The incident angle for all measurements was zero.

The visible light transmittance was the measurement of visible light (orlight energy) that was transmitted through a sample material whenvisible light within the spectral range of 400 nanometers to 700nanometers was directed through the material. The results of alltransmittance over the range of 400 nanometers to 700 nanometers wascollected and recorded. For each sample, a minimum value for the visiblelight transmittance was determined for this range.

The visible light reflectance was a measurement of the visible light (orlight energy) that was reflected by a sample material when visible lightwithin the spectral range of 400 nanometers to 700 nanometers wasdirected through the material. The results of all reflectance over therange of 400 nanometers to 700 nanometers was collected and recorded.For each sample, a minimum value for the visible light reflectance wasdetermined for this range.

Various embodiments of the present disclosure are described below ineach of the sets of aspects. In each of the clause sets, “disposing” canbe replaced with “operably disposing.”

It should be noted that ratios, concentrations, amounts, and othernumerical data may be expressed herein in a range format. It is to beunderstood that such a range format is used for convenience and brevity,and thus, should be interpreted in a flexible manner to include not onlythe numerical values explicitly recited as the limits of the range, butalso to include all the individual numerical values or sub-rangesencompassed within that range as if each numerical value and sub-rangeis explicitly recited. To illustrate, a concentration range of “about0.1 percent to about 5 percent” should be interpreted to include notonly the explicitly recited concentration of about 0.1 weight percent toabout 5 weight percent but also include individual concentrations (e.g.,1 percent, 2 percent, 3 percent, and 4 percent) and the sub-ranges(e.g., 0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4percent) within the indicated range. The term “about” can includetraditional rounding according to significant figures of the numericalvalue. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ toabout ‘y’”.

Many variations and modifications may be made to the above-describedembodiments. All such modifications and variations are intended to beincluded herein within the scope of this disclosure and protected by thefollowing claims.

The clauses are:
 1. An article, comprising a SC filament having aplurality of optical elements and the fragments thereof randomlydistributed throughout the SC filament, wherein the plurality of opticalelements and the fragments thereof impart an optical effect to thefilament, wherein the article is an article of footwear, an article ofapparel, or an article of sporting equipment.
 2. The article of claim 1,wherein the optical effect is a structural color and is not iridescentor metallic.
 3. The article of claim 1, wherein the optical effect is aniridescent appearance.
 4. The article of claim 1, wherein the opticaleffect is a metallic appearance.
 5. The article of claim 1, wherein theoptical element and the fragments thereof are a layered structure thathas two or more layers stacked in a z-dimension perpendicular to theplane of the layered structures.
 6. The article of claim 1, wherein theplurality of optical elements and the fragments thereof dispersed in theSC filament has, individually, an average width and an average length ofabout 400 nanometers or more, and wherein the plurality of dispersedoptical elements and the fragments thereof in the filament has anaverage thickness of about 200 nanometers or more.
 7. The article ofclaim 1, wherein the plurality of optical elements and the fragmentsthereof make up at least 1 percent by weight of a total weight of thefilament.
 8. The article of claim 1, wherein the plurality of theoptical elements and the fragments thereof on the SC filament covers atleast 25 percent of a total surface area of the filament.
 9. The articleof claim 1, wherein the optical effect imparted to the filament isvisible to a viewer having 20/20 visual acuity and normal color visionfrom a distance of about 1 meter from the article.
 10. The article ofclaim 1, wherein the structurally colored thermoplastic materialcomprises at least one thermoplastic polymer.
 11. The article of claim1, wherein the optical element is single layer reflector, a single layerfilter, a multilayer reflector or a multilayer filter.
 12. The articleof claim 1, wherein the multilayer reflector has at least two layers,including at least two adjacent layers having different refractiveindices.
 13. The article of claim 1, wherein at least one of the layersof the multilayer reflector comprises a material selected from the groupconsisting of: silicon dioxide, titanium dioxide, zinc sulfide,magnesium fluoride, tantalum pentoxide, and a combination thereof. 14.The article of claim 1, wherein the optical effect imparts two or moredifferent hues to the article when the article is viewed from at leasttwo different angles 15 degrees apart.
 15. The article of claim 1,wherein the optical effect imparts a single hue when the articles isviewed from at least two different angles 15 degrees apart.
 16. Thearticle of claim 1, further comprising a textured surface on a firstside of the optical element, wherein the textured surface has aplurality of profile features and a plurality of flat areas.
 17. Thearticle of claim 16, wherein both the length and the width of theprofile feature is greater than 500 micrometers.
 18. The article ofclaim 16, wherein the height of the profile features can be greater than50 micrometers.
 19. The article of claim 16, wherein at least one of thelength and width of the profile feature is in the nanometer range, whilethe other of the length and the width of the profile feature is in themicrometer range.
 20. The article of claim 16, wherein spatialorientation of the profile features is a semi-random pattern or a setpattern.